Silver halide photographic material and hydroxamic acid-base compound for use therein

ABSTRACT

A silver halide photographic material is disclosed, comprising a support having thereon at least one light-sensitive silver halide emulsion layer, wherein said silver halide photographic material contains a compound by formula (IA), or which contains at least one hydroxamic acid compound having a bicyclo ring as a partial structure and represented by formula (IB).

FIELD OF THE INVENTION

The present invention relates to a light-sensitive silver halidephotographic material, more specifically, the present invention relatesto a photographic material less changeable in the photographiccapability after storage and less changeable in the photographiccapability after photographing until development processing.

Further, the present invention relates to a silver halide photographicmaterial causing less generation of fog.

Furthermore, the present invention relates to a novel hydroxamicacid-base compound capable of providing photographically useful effects.

BACKGROUND OF THE INVENTION

Silver halide photographic materials are not only demanded to have highsensitivity but also be less changeable in the photographic capabilityduring storage after the preparation of the photographic material andalso less changeable in the photographic capability after photographinguntil development processing.

Out of changes in the photographic capability after photographing untildevelopment processing, with respect to the prevention oflatensification, JP-A-59-162546 (the term "JP-A" as used herein means an"unexamined published Japanese patent application") discloses a methodof using a hardening agent having an active vinyl group in combinationwith a triazine-base compound.

However, the above-described method is insufficient in the preventioneffect and a further improvement has been demanded.

On the other hand, full color photographic materials use a plurality ofemulsions different in the spectral sensitivity as a superposed layerstructure, thereby achieving the object of full color photograph. Theemulsions used therein have been fairly improved, however, they arestill unsatisfactory because fogging of the latent image orintensification/regression is caused. In order to improve storability ofthe emulsion, for example, 2-hydroxamino-1,3,5-triazines are effective.However, the layers are different in the storability from each otherdepending upon the emulsion used therein. Accordingly, in recent years,it is being rather strongly demanded to improve storability of a latentimage of a specific emulsion layer.

Many of known 2-hydroxylamine-1,3,5-triazines diffuse and act on theemulsion in the layer other than the objective layer and as a result,the balance in the gradation among respective layers is lost. Further,hydroxamic acids having a specific structure described in U.S. Pat. Nos.4,339,515 and 4,330,606, JP-A-59-198453 and JP-A-3-293666 are used toimprove storability of a color image or as a nucleophilic agent anddifferent from the present invention in the use object. Moreover, theabove-described hydroxamic acids are insufficient in causing action onlyon an emulsion in a specific layer. Accordingly, a method for greatlyimproving the storability of a latent image only in the objective layerhas been keenly demanded.

The present invention provides a method for improving storability of anemulsion in a specific layer and stability of a latent image.

In order to overcome the above-described problems, the present inventorshave made extensive investigations on the method for improvingstorability of an emulsion produced and storability of a latent image,in particular, on the structure of compounds, and as a result, they havefound a novel hydroxamic acid-base compound having a specific structurefor use in the present invention.

The compound for use in the present invention is found, when added to asilver halide photographic material, able to achieve the objects of thepresent invention without changing the hue of the dye formed, affectingthe dye formation speed of couplers, accelerating the decomposition ofthe coupler or the dye formed, deteriorating the layer strength orfogging the emulsion.

Out of the compounds for use in the present invention, the compoundsrepresented by formulae (IVA), (IVB), (VA) and (VB) are completely novelcompounds which have not known in the past. These compounds are firstfound to be photographically useful after investigations by the presentinventors.

SUMMARY OF THE INVENTION

A first object of the present invention is to provide a compound highlyeffective in improving the storability of a silver halide emulsion andstorability of a latent image.

A second object of the present invention is to provide a method forimproving storability of a latent image using the above-describedcompound.

A third object of the present invention is to provide a compound capableof improving storability only of a latent image in a specific layer.

A fourth object of the present invention is to provide a method forimproving storability of a latent image using the above-describedcompound.

A fifth object of the present invention is to provide a compound capableof, when added, improving storability of a latent image withoutadversely affecting various photographic properties.

A sixth object of the present invention is to provide a method forimproving storability of a latent image using the above-describedcompound.

The objects of the present invention have been achieved by the followingmaterials and compounds:

(1) a silver halide photographic material comprising a support havingthereon at least one light-sensitive silver halide emulsion layer,wherein said silver halide photographic material contains a compoundrepresented by formula (IA): ##STR1## wherein R^(1a) represents ahydrogen atom, a substituted or unsubstituted alkyl group having from 1to 20 carbon atoms, a substituted or unsubstituted alkenyl group havingfrom 2 to 20 carbon atoms or a substituted or unsubstituted aryl grouphaving from 6 to 20 carbon atoms;

R^(2a) represents an alkenyl group having a total carbon number of 4 ormore or a cycloalkenyl group having a total carbon atom number of 6 ormore;

provided that when R^(2a) is a styryl group, R^(1a) is a substituted orunsubstituted alkyl group having from 1 to 20 carbon atoms, asubstituted or unsubstituted alkenyl group having from 2 to 20 carbonatoms or a substituted or unsubstituted aryl group having from 6 to 20carbon atoms; and

when R^(2a) is an alkenyl group having a total carbon number of 17 ormore, R^(1a) is a hydrogen atom, a substituted or unsubstituted alkylgroup having 7 or more carbon atoms, a substituted or unsubstitutedalkenyl group having 7 or more carbon atoms or a substituted orunsubstituted aryl group having from 6 to 20 carbon atoms;

(2) a silver halide photographic material as described in item (1),wherein the compound represented by formula (IA) has a structurerepresented by formula (IIA) or (IIIA): ##STR2## wherein in formula(IIA), R^(1a) represents a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms or a substituted orunsubstituted alkenyl group having from 2 to 20 carbon atoms;

Q^(1a) represents an atomic group necessary for forming a cycloalkenylgroup by combining with the carbon atoms at both terminals;

R^(3a) and R^(4a), which may be the same or different, each representsan alkyl group having from 1 to 22 carbon atoms, an aryl group havingfrom 6 to 20 carbon atoms, an alkenyl group having from 3 to 22 carbonatoms, a carboxyl group, a cyano group, an acyl group having from 2 to20 carbon atoms, an aminocarbonyl group having from 1 to 37 carbonatoms, an alkoxycarbonyl group having from 2 to 20 carbon atoms, anaryloxycarbonyl group having from 7 to 20 carbon atoms or a heterocyclicgroup having from 3 to 20 carbon atoms;

R^(a) represents an alkyl group, an aryl group, an alkoxy group, anaryloxy group, an alkenyl group, a carboxyl group, a cyano group, asulfamoyl group, an acyl group, a carbamoyl group, an alkoxycarbonylgroup, an aryloxycarbonyl group, an acylamino group, analkoxycarbonylamino group, an aryloxycarbonylamino group, analkylsulfonylamino group, an arylsulfonylamino group, anaminocarbonylamino group, a sulfamoylamino group, an amino group, aheterocyclic oxy group, an alkylthio group, an arylthio group, aheterocyclic thio group, a heterocyclic group, an alkylsulfonyl group oran arylsulfonyl group; and

na represents 0 or a positive integer, and when na is 0, R^(a) is ahydrogen atom and when na is 2 or greater, the R^(a) groups in pluralitymay be the same or different; and

in formula (IIIA), R^(1a) represents a hydrogen atom, a substituted orunsubstituted alkyl group having from 1 to 20 carbon atoms or asubstituted or unsubstituted alkenyl group having from 2 to 20 carbonatoms,

R^(3a), R^(4a) and R^(5a), which may be the same or different, each hasthe same meaning as R^(3a) or R^(4a) of formula (IIA);

when R^(4a) is a phenyl group, R^(1a) is a substituted or unsubstitutedalkyl group having from 1 to 22 carbon atoms, a substituted orunsubstituted alkenyl group having from 2 to 22 carbon atoms or asubstituted or unsubstituted aryl group having from 6 to 20 carbonatoms; and

R^(3a) and R^(4a) and/or R^(4a) and R^(5a) and/or R^(5a) and R^(1a) maybe combined with each other to form a 5- or 6-membered ring structure;

(3) a compound represented by formula (IVA) or (VA): ##STR3## wherein informula (IVA), R^(1a), R^(3a) and R^(4a) have the same meaning asR^(1a), R^(3a) and R^(4a) of formula (IIA) in item (2), respectively;

R^(6a), R^(7a), R^(8a), R^(9a), R^(10a), R^(11a), R^(12a), which may bethe same or different, each represents a hydrogen atom, an alkyl grouphaving from 1 to 20 carbon atoms, an alkoxycarbonyl group having from 2to 30 carbon atoms, an aminocarbonyl group having from 1 to 30 carbonatoms or an aryloxycarbonyl group having from 7 to 30 carbon atoms; and

in formula (VA), R^(1a) has the same meaning as R^(1a) of formula (IIIA)in item (2);

R^(3a), R^(4a) and R^(5a), which may be the same or different, eachrepresents a hydrogen atom, an alkyl group having from 1 to 20 carbonatoms, an aryl group having from 6 to 22 carbon atoms, an alkoxycarbonylgroup having from 2 to 30 carbon atoms, an aryloxycarbonyl group havingfrom 7 to 30 carbon atoms or an aminocarbonyl group having from 1 to 30carbon atoms; and

when R^(4a) is a phenyl group, R^(1a) is a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms or a substituted orunsubstituted alkenyl group having from 2 to 20 carbon atoms;

(4) a silver halide photographic material comprising a support havingthereon at least one silver halide emulsion layer, which contains atleast one hydroxamic acid compound having a bicyclo ring as a partialstructure;

(5) a silver halide photographic material as described in item (4),wherein said hydroxamic acid compound is represented by the followingformula (IB): ##STR4## wherein R^(1b) represents a hydrogen atom, asubstituted or unsubstituted alkyl group having from 1 to 30 carbonatoms, a substituted or unsubstituted cycloalkyl group having from 5 to30 carbon atoms, a substituted or unsubstituted alkenyl group havingfrom 3 to 30 carbon atoms or a substituted or unsubstituted cycloalkenylgroup having from 5 to 30 carbon atoms, and R^(2b) represents asubstituted or unsubstituted bicycloalkyl group having from 5 to 40carbon atoms or a substituted or unsubstituted bicycloalkenyl grouphaving from 5 to 40 carbon atoms;

(6) a silver halide photographic material as described in item (5),wherein the compound represented by formula (IB) has a structurerepresented by formula (IIB) or (IIIB): ##STR5## wherein R^(1b)represents a hydrogen atom, a substituted or unsubstituted alkyl grouphaving from 1 to 30 carbon atoms, a substituted or unsubstitutedcycloalkyl group having from 5 to 30 carbon atoms, a substituted orunsubstituted alkenyl group having from 3 to 30 carbon atoms or asubstituted or unsubstituted cycloalkenyl group having from 5 to 30carbon atoms;

R^(3b) and R^(4b), which may be the same or different, each represents ahydrogen atom or a substituted or unsubstituted alkyl group having from1 to 30 carbon atoms; and

Q^(1b), Q^(2b) and Q^(3b) each independently represents an atomic groupnecessary for forming a bicyclo ring by combining with the carbon atomsat both terminals; and

(7) a hydroxamic acid compound represented by formula (IVB) or (VB):##STR6## wherein X^(b) represents --OR^(5b) or --N(R^(5b))(R^(6b))(wherein R^(5b) and R^(6b), which may be the same or different, eachrepresents a hydrogen atom, a substituted or unsubstituted alkyl grouphaving from 1 to 30 carbon atoms, a substituted or unsubstitutedcycloalkyl group having from 5 to 30 carbon atoms or a substituted orunsubstituted aryl group having from 6 to 30 carbon atoms, and R^(5b)and R^(6b) are combined with each other to form a ring structure); and

R^(1b) represents a hydrogen atom or an alkyl group having from 1 to 6carbon atoms.

DETAILED DESCRIPTION OF THE INVENTION

Formula (IA) is described in detail below.

In formula (IA), R^(1a) represents a hydrogen atom, a substituted orunsubstituted alkyl group having from 1 to 20 carbon atoms, asubstituted or unsubstituted alkenyl group having from 2 to 20 carbonatoms or a substituted or unsubstituted aryl group having from 6 to 20carbon atoms.

Specific examples of R^(1a) include a hydrogen atom and as an alkylgroup, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl,n-pentyl, isopentyl, neopentyl, n-hexyl and n-dodecyl.

Examples of the substituent of the alkyl group include an alkyl group,an alkenyl group, an aryl group, a heterocyclic group, a halogen atom,an alkoxy group, an aryloxy group, an alkylthio group, an arylthiogroup, a cyano group, a nitro group, an alkoxycarbonyl group, anaryloxycarbonyl group, a hydroxyl group, an acyl group, an acyloxygroup, an alkylsulfonyl group, an arylsulfonyl group, an acylaminogroup, an alkylsulfonamido group and an arylsulfonamido group. Specificexamples thereof include 2-chloroethyl, 2-methoxyethyl, 2-cyanoethyl,2-ethoxycarbonylethyl, 3-methylthiopropyl, 2-acetylaminoethyl,3-hydroxypropyl, 2-acetyloxyethyl, 3-chloroethyl and 3-methoxyethyl.Specific examples of the alkenyl group include allyl, prenyl,homoprenyl, geranyl and oleyl.

Specific examples of the aryl group represented by R^(1a) includephenyl, o-chlorophenyl, m-methoxyphenyl, naphthyl, p-diethylaminophenyland p-(n)-dodecylphenyl.

R^(2a) represents an alkenyl group having a total carbon number of 4 ormore or a cycloalkenyl group having a total carbon number of 6 or more.

Specific examples of the alkenyl group include a geranyl group, ageranylgeranyl group, an oleyl group, a substituted vinyl group (havingfrom 4 to 30 carbon atoms, e.g., cisoctylvinyl, transoctylvinyl,transdodecylvinyl) and prenyl.

In the nomenclature, the cycloalkenyl group is a monocyclic groupcontaining one double bond, however, in the present invention, thecycloalkenyl group includes a cycloalkadienyl group having a relation tothe cycloalkenyl group.

Specific examples of the cycloalkenyl group include 2-cyclohexenyl,3-cyclohexenyl, 2,4-cyclohexadienyl and 2-cyclopentyl.

The compound for use in the present invention preferably has a structurerepresented by formula (IIA) or (IIIA).

In formula (IIA), R^(1a) represents a hydrogen atom, a substituted orunsubstituted alkyl group having from 1 to 20 carbon atoms or asubstituted or unsubstituted alkenyl group having from 3 to 20 carbonatoms.

Specific examples thereof include those described in formula (IA).

R^(3a) and R^(4a), which may be the same or different, eachindependently represents a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 22 carbon atoms, an aryl group having from6 to 20 carbon atoms, an alkenyl group having from 3 to 22 carbon atoms,a carboxyl group, a cyano group, an acyl group having from 2 to 20carbon atoms, an aminocarbonyl group having from 1 to 37 carbon atoms,an alkoxycarbonyl group having from 2 to 20 carbon atoms, anaryloxycarbonyl group having from 7 to 20 carbon atoms or a heterocyclicgroup having from 3 to 20 carbon atoms.

Specific examples thereof include those described below for R^(a).

R^(a) represents an alkyl group, an aryl group, an alkoxy group, anaryloxy group, an alkenyl group, a carboxyl group, a cyano group, asulfamoyl group, an acyl group, a carbamoyl group, an alkoxycarbonylgroup, an aryloxycarbonyl group, an acylamino group, an alkoxycarbonylgroup, an aryloxycarbonylamino group, an alkylsulfonylamino group, anarylsulfonylamino group, an aminocarbonylamino group, a sulfamoylaminogroup, an amino group, a heterocyclic oxy group, an alkylthio group, anarylthio group, a heterocyclic thio group, a heterocyclic group, analkylsulfonyl group or an arylsulfonyl group.

Examples thereof include an aryl group (inclusive of a substituted arylgroup, preferably having from 6 to 20 carbon atoms, e.g., phenyl,m-acetylaminophenyl, p-methoxyphenyl), an alkyl group (inclusive of asubstituted alkyl group, preferably having from 1 to 30 carbon atoms,e.g., methyl, ethyl, isopropyl, t-butyl, n-octyl, n-dodecyl), a cyanogroup, a carboxyl group, an acyl group (preferably having from 1 to 30carbon atoms, e.g., acetyl, pivaloyl, benzoyl, furoyl, 2-pyridyl), acarbamoyl group (preferably having from 1 to 30 carbon atoms, e.g.,methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, n-octylcarbamoyl),an alkoxycarbonyl group (inclusive of a substituted alkoxycarbonylgroup, preferably having from 2 to 30 carbon atoms, e.g.,methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl), an aryloxycarbonylgroup (including a substituted aryloxycarbonyl group, preferably havingfrom 7 to 30 carbon atoms, e.g., phenoxycarbonyl,p-methoxyphenoxycarbonyl, m-chlorophenoxycarbonyl,o-methoxyphenoxycarbonyl), an acylamino group for example, analkylcarbonylamino group preferably having from 1 to 30 carbon atoms(inclusive of a substituted alkylcarbonylamino group, e.g., formylamino,acetylamino, propionylamino, cyanoacetylamino), an arylcarbonylaminogroup preferably having from 7 to 30 carbon atoms (inclusive of asubstituted arylcarbonylamino group, e.g., benzoylamino, p-toluylamino,pentafluorobenzoylamino, m-methoxybenzoylamino), and aheterylcarbonylamino group preferably having from 4 to 30 carbon atoms(inclusive of a substituted heterylcarbonylamino group, e.g.,2-pyridylcarbonylamino, 3-pyridylcarbonylamino, furoylamino)!, analkoxycarbonylamino group (inclusive of a substitutedalkoxycarbonylamino group, preferably having from 2 to 30 carbon atoms,e.g., methoxycarbonylamino, ethoxycarbonylamino,methoxyethoxycarbonylamino), an aryloxycarbonylamino group (inclusive ofa substituted aryloxycarbonylamino group, preferably having from 7 to 30carbon atoms, e.g., phenoxycarbonylamino, p-methoxyphenoxycarbonylamino,p-methylphenoxycarbonylamino, m-chlorophenoxycarbonylamino,o-chlorophenoxycarbonylamino), an aminocarbonylamino group (preferablyhaving from 1 to 30 carbon atoms, e.g., methylaminocarbonylamino,ethylaminocarbonylamino, anilinocarbonylamino,dimethylaminocarbonylamino), a sulfamoylamino group (preferably havingfrom 1 to 30 carbon atoms, e.g., methylaminosulfonylamino,ethylaminosulfonylamino, anilinosulfonylamino), an amino group(inclusive of an anilino group, preferably having from 0 to 30 carbonatoms, e.g., amino, methylamino, dimethylamino, ethylamino,diethylamino, n-butylamino, anilino), an alkoxy group (inclusive of asubstituted alkoxy group, preferably having from 1 to 30 carbon atoms,e.g., methoxy, ethoxy, isopropoxy, n-butoxy, methoxyethoxy, isopropoxy,n-dodecyloxy), an aryloxy group (inclusive of a substituted aryloxygroup, preferably having from 6 to 30 carbon atoms, e.g., phenoxy,m-chlorophenoxy, p-methoxyphenoxy, o-methoxyphenoxy), a heteryloxy group(inclusive of a substituted heteryloxy group, preferably having from 3to 30 carbon atoms, e.g., tetrahydropyranyloxy, 3-pyridyloxy,2-(1,3-benzimidazolyl)oxy), an alkylthio group (inclusive of asubstituted alkylthio group, preferably having from 1 to 30 carbonatoms, e.g., methylthio, ethylthio, n-butylthio, t-butylthio), anarylthio group (inclusive of a substituted arylthio group, preferablyhaving from 6 to 30 carbon atoms, e.g., phenylthio), a heterylthio group(inclusive of a substituted heterylthio group, preferably having from 3to 30 carbon atoms, e.g., 2-pyridylthio, 2-(1,3-benzoxazolyl)thio,1-hexadecyl-1,2,3,4-tetrazolyl-5-thio,1-(3-N-octadecylcarbmoyl)phenyl-1,2,3,4-tetrazolyl-5-thio), aheterocyclic group (inclusive of a substituted heterocyclic group,preferably having from 3 to 30 carbon atoms, e.g., thiadiazolyl,pyrazolyl), an alkenyl group (preferably having from 3 to 18 carbonatoms, e.g., vinyl, allyl, prenyl), a sulfamoyl group (preferably havingfrom 0 to 36 carbon atoms, e.g., methylsulfamoyl, dimethylsulfamoyl,dioctylsulfamoyl), an alkylsulfonylamino group (preferably having from 1to 18 carbon atoms, e.g., methanesulfonylamino, n-butanesulfonylamino),an arylsulfonylamino group (preferably having from 6 to 18 carbon atoms,e.g., benzenesulfonylamino, p-toluenesulfonylamino), an alkylsulfonylgroup (preferably having from 1 to 18 carbon atoms, e.g.,methanesulfonyl, ethanesulfonyl, n-octanesulfonyl) and an arylsulfonylgroup (preferably having from 6 to 18 carbon atoms, e.g.,benzenesulfonyl, p-toluenesulfonyl).

na represents 0 or a positive integer, and when na is 0, R^(a) is ahydrogen atom and when na is 2 or greater, the R^(a) groups in pluralitymay be the same or different.

na is preferably 1 or greater, most preferably 1.

Q^(1a) represents an atomic group necessary for forming a cycloalkenylgroup by combining with the carbon atoms at both terminals.

Specific examples thereof are described below. ##STR7##

The cycloalkenyl group is a monovalent group obtained by removing oneR^(a) group from the structure represented by formula (IIA)-1, (IIA)-2,(IIA)-3, (IIA)-4, (IIA)-5 or (IIA)-6.

The R^(a) groups may be the same or different and each independently hasthe same meaning as R^(a) in formula (IIA).

R^(3a) and R^(4a) have the same meaning as R^(3a) and R^(4a) in formula(IIA), respectively.

Among formulae (IIA)-1 to (IIA)-6, preferred are formulae (IIA)-1 and(IIA)-4.

In a preferred embodiment of formula (IIA), R^(1a) is a hydrogen atom ora substituted or unsubstituted alkyl group having from 1 to 20 carbonatoms, Q^(1a) forms a structure of formula (IIA)-1 or (IIA)-4, R^(3a)and R^(4a), which may be the same or different, each independently is ahydrogen atom, an alkyl group having from 1 to 6 carbon atoms, analkoxycarbonyl group having from 2 to 23 carbon atoms or anaminocarbonyl group having from 3 to 37 carbon atoms, R^(a) is an alkylgroup having from 1 to 22 carbon atoms, an alkoxycarbonyl group havingfrom 2 to 23 carbon atoms, an aminocarbonyl group having from 3 to 27carbon atoms or an aryloxycarbonyl group having from 7 to 26 carbonatoms, and na is 0 or 1.

In a more preferred embodiment of formula (IIA), R^(1a) is a substitutedor unsubstituted alkyl group having from 1 to 20 carbon atoms, Q^(1a)forms a structure of formula (IIA)-1, R^(3a) and R^(4a), which may bethe same or different, each independently is a hydrogen atom or asubstituted or unsubstituted alkyl group having from 1 to 6 carbonatoms, R^(a) is an alkoxycarbonyl group having from 2 to 23 carbon atomsor an aminocarbonyl group having from 3 to 27 carbon atoms, and na is 1.

A still more preferred embodiment of formula (IIA) is the structurerepresented by formula (IVA): ##STR8## wherein R^(1a) represents ahydrogen atom or a substituted or unsubstituted alkyl group having from1 to 20 carbon atoms, R^(3a) and R^(4a) have the same meaning as R^(3a)and R^(4a) in formula (IIA), respectively, R^(6a), R^(7a), R^(8a),R^(9a), R^(10a), R^(11a) and R^(12a), which may be the same ordifferent, each independently represents a hydrogen atom or has the samemeaning as R^(a) in formula (IIA), and one of R^(3a), R^(4a), R^(6a),R^(7a), R^(8a), R^(9a) and R^(10a) is an alkoxycarbonyl group havingfrom 1 to 23 carbon atoms or an aminocarbonyl group having from 3 to 37carbon atoms.

In a preferred embodiment of formula (IVA), R^(1a) is a hydrogen atom ora substituted or unsubstituted alkyl group having from 1 to 20 carbonatoms, R^(3a) and R^(4a), which may be the same or different, each is ahydrogen atom or a substituted or unsubstituted alkyl group having from1 to 30 carbon atoms, R^(6a), R^(7a), R^(8a), R^(9a), R^(11a) andR^(12a) all are a hydrogen atom, R^(10a) is an alkoxycarbonyl grouphaving from 2 to 23 carbon atoms or an aminocarbonyl group having from 3to 37 carbon atoms.

In particular, R^(10a) and the --CON(R^(1a))--OH group are in a cisrelation with each other.

R^(10a) is preferably an alkoxycarbonyl group rather than anaminocarbonyl group.

R^(1a) is preferably an unsubstituted alkyl group having from 1 to 6carbon atoms.

In a most preferred embodiment of formula (IVA), R^(1a) is anunsubstituted alkyl group having from 1 to 6 carbon atoms, R^(3a),R^(4a), R^(6a), R^(7a), R^(8a), R^(9a), R^(11a) and R^(12a) all are ahydrogen atom, R^(10a) is an unsubstituted alkoxycarbonyl group havingfrom 12 to 23 carbon atoms, and R^(10a) and the --CON(R^(1a))--OH groupare in a cis relation with each other.

In formula (IIIA), R^(3a), R^(4a) and R^(5a), which may be the same ordifferent, each is the same as R^(3a) or R^(4a) in formula (IIA).

Specific examples thereof include those described above for R^(3a) andR^(4a) in formula (IIA). When R^(4a) is a phenyl group, R^(1a) is asubstituted or unsubstituted alkyl group having from 1 to 22 carbonatoms, a substituted or unsubstituted alkenyl group having from 2 to 22carbon atoms or a substituted or unsubstituted aryl group having from 6to 20 carbon atoms.

A preferred embodiment of formula (IIIA) is the structure represented byformula (VA).

In formula (VA), R^(1a) has the same meaning as R^(1a) in formula(IIIA), R^(3a), R^(4a) and R^(5a), which may be the same or different,each independently represents a hydrogen atom, an alkyl group havingfrom 1 to 20 carbon atoms, an aryl group having from 6 to 22 carbonatoms, an alkoxycarbonyl group having from 2 to 30 carbon atoms, anaryloxycarbonyl group having from 7 to 30 carbon atoms or anaminocarbonyl group having from 1 to 30 carbon atoms.

When R^(4a) is a phenyl group, R^(1a) is a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms or a substituted orunsubstituted alkenyl group having from 2 to 22 carbon atoms.

In a preferred embodiment of formula (VA), R^(1a) is a hydrogen atom ora substituted or unsubstituted alkyl group having from 1 to 20 carbonatoms, R^(4a) and R^(5a), which may be the same or different, eachindependently is a hydrogen atom, an alkoxycarbonyl group having from 2to 23 carbon atoms or an aminocarbonyl group having from 3 to 37 carbonatoms, and R^(3a) is a hydrogen atom.

In a most preferred embodiment of formula (VA), R^(1a) is a substitutedor unsubstituted alkyl group having from 1 to 6 carbon atoms, R^(3a) isa hydrogen atom, and one of R^(4a) and R^(5a) is an alkoxycarbonyl grouphaving from 14 to 23 carbon atoms and the other is a hydrogen atom.

The compound represented by formula (IA) has a molecular weight, when itis used to improve storability of a specific layer, of preferably 300 ormore, more preferably 350 or more and most preferably 450 or more.

In this case, the compound for use in the present invention should besubstantially insoluble in water so that it does not diffuse into thegelatin layer. The term "substantially insoluble in water" as usedherein means that the solubility at 25° C. in water is 5% or less,preferably 1% or less.

Some raw materials (for example, acid anhydrides which will be describedlater or alcohols) for use in the synthesis of the compound for use inthe present invention are available only as a mixture of isomers orhomologs, and accordingly, in some cases, it is easy to synthesize thecompound for use in the present invention as a mixture of isomers orhomologs. In this case, the compound for use in the present invention ispreferably added as the mixture to the silver halide photographicmaterial.

Specific examples of the compound for use in the present invention areset forth below, however, the present invention is by no means limitedthereto.

    __________________________________________________________________________     ##STR9##                                                                     Compound                                                                      No.   R.sup.1a                                                                             X.sup.a      R.sup.2a                                                                          R.sup.3a                                                                         R.sup.6a                                                                         R.sup.7a                                  __________________________________________________________________________    A-1   CH.sub.3                                                                             OC.sub.18 H.sub.37.sup.-n                                                                  H   H  H  H                                         A-2   C.sub.2 H.sub.5                                                                      "            "   "  "  "                                         A-3   C.sub.3 H.sub.7.sup.-n                                                               "            "   "  "  "                                         A-4                                                                                  ##STR10##                                                                           OC.sub.16 H.sub.33.sup.-n                                                                  "   "  "  "                                         A-5   C.sub.5 H.sub.11.sup.-n                                                              "            "   "  "  "                                         A-6   CH.sub.2 CH.sub.2 CN                                                                 "            "   "  "  "                                         A-7   C.sub.8 H.sub.17.sup.-n                                                              "            "   "  "  "                                         A-8   CH.sub.3                                                                             OC.sub.20 H.sub.41.sup.-n                                                                  H   H  H  H                                         A-9   H      OC.sub.22 H.sub.45.sup.-n                                                                  "   "  "  "                                         A-10  C.sub.3 H.sub.7.sup.-n                                                               OC.sub.14 H.sub.29.sup.-n                                                                  "   "  "  "                                         A-11  C.sub.3 H.sub.7.sup.-n                                                               A            "   "  "  "                                         A-12  CH.sub.3                                                                             B            "   "  "  "                                         A-13  C.sub.5 H.sub.11.sup.-n                                                              OC.sub.10 H.sub.21.sup.-n                                                                  "   "  "  "                                         A-14  CH.sub.3                                                                             OC.sub.18 H.sub.37.sup.-n                                                                  CH.sub.3                                                                          CH.sub.3                                                                         H  H                                         A-15  CH.sub.3                                                                             OC.sub.16 H.sub.33.sup.-n                                                                  CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                  A-16  CH.sub.3                                                                              ##STR11##   H   H  H  H                                         A-17  C.sub.2 H.sub.5                                                                       ##STR12##   "   "  "  "                                         A-18  C.sub.8 H.sub.17.sup.-n                                                               ##STR13##   "   "  "  "                                         A-19                                                                                 ##STR14##                                                              A-20                                                                                 ##STR15##                                                              A-21                                                                                 ##STR16##                                                              A-22                                                                                 ##STR17##                                                              __________________________________________________________________________     ##STR18##                                                                    Compound                                                                      No.         R.sup.1a     X.sup.a                                              __________________________________________________________________________    A-23        CH.sub.3     OC.sub.18 H.sub.37.sup.-n                            A-24        C.sub.2 H.sub.5                                                                            OC.sub.16 H.sub.33.sup.-n                            A-25        C.sub.3 H.sub.7.sup.-n                                                                     OC.sub.14 H.sub.29.sup.-n                            A-26        C.sub.4 H.sub.9.sup.-n                                                                     OC.sub.22 H.sub.45.sup.-n                            A-27                                                                                       ##STR19##   OC.sub.18 H.sub.37.sup.-n                            A-28        C.sub.8 H.sub.17.sup.-n                                                                    A                                                    A-29        CH.sub.3     A                                                    A-30        C.sub.2 H.sub.5                                                                            B                                                    A-31        H                                                                                           ##STR20##                                           A-32        CH.sub.3                                                                                    ##STR21##                                           __________________________________________________________________________     ##STR22##                                                                    Compound                                                                      No.      R.sup.1a       X.sup.a                                               __________________________________________________________________________    A-33     C.sub.2 H.sub.5                                                                              OC.sub.18 H.sub.37.sup.-n                             A-34     CH.sub.3       OC.sub.16 H.sub.33.sup.-n                             A-35                                                                                    ##STR23##     OC.sub.22 H.sub.45.sup.-n                             A-36     C.sub.4 H.sub.9.sup.-n                                                                       OC.sub.18 H.sub.37.sup.-n                             A-37     C.sub. H.sub.2 C.sub. H.sub.2 CN                                                             A                                                     A-38     CH.sub.3       B                                                     A-39     CH.sub.3                                                                                      ##STR24##                                            A-40     C.sub.2 H.sub.5                                                                               ##STR25##                                            A-41                                                                                    ##STR26##                                                                                    ##STR27##                                            A-42     H              OC.sub.18 H.sub.37.sup.-n                             A-43                                                                                    ##STR28##                                                           A-44                                                                                    ##STR29##                                                           A-45                                                                                    ##STR30##                                                           A-46                                                                                    ##STR31##                                                                     ##STR32##                                                                     ##STR33##                                                           __________________________________________________________________________

The synthesis method in general of the compound for use in the presentinvention is described below.

The compound for use in the present invention is obtained by condensinga corresponding carboxylic acid chloride with hydroxylamine or aN-substituted hydroxylamine. The carboxylic acid chloride can be easilyobtained, when the corresponding carboxylic acid is easily available, bytreating the carboxylic acid with thionyl chloride or oxalyl chloride.In the case of a complex carboxylic acid, a carboxylic acid issynthesized by a method according to respective cases and then treatedwith thionyl chloride or oxalyl chloride. The carboxylic acid can besynthesized in accordance with the following synthesis examples.

On the other hand, with respect to N-alkylhydroxylamine, those where thealkyl is a methyl group are commercially available and others can besynthesized according to the following methods. ##STR34##

Acetone is added to hydroxylamine to convert it into acetoxime and theacetoxime is reacted with an alkylating agent to synthesize N-alkyl form(nitron). Thereafter, acetone is eliminated by performing acid treatmentand as a result, N-alkylhydroxylamine is obtained.

The present invention is described in greater detail by referring to thefollowing synthesis examples of the compound for use in the presentinvention.

SYNTHESIS EXAMPLE 1A:

Synthesis of Compound A-1: ##STR35## Step 1:

Cis-4-cyclohexene-1,2-dicarboxylic anhydride (9.13 g (60 mmol)) and 16.2g (60 mmol) of stearyl alcohol were mixed and the mixture was reacted at120° C. for 2 hours and cooled to obtain Intermediate A.

Step 2:

To a mixture of the entire amount of Intermediate A, 20 ml of methylenechloride and 0.5 ml of dimethylformamido, 8.6 g (72 mmol) of thionylchloride was added, and the resulting mixture was reacted at 30° C. for1 hour. After completion of the reaction, the remaining thionyl chlorideand methylene chloride was removed under reduced pressure by means of anaspirator to obtain 23.5 g (55.6 mmol) of Intermediate B (yield: 92.7%).

Step 3:

To 7.52 g (90 mmol) of N-methylhydroxylamine hydrochloride, 3.6 g (90mmol) of sodium hydroxide, 100 ml of water, 15.1 g (180 mmol) of sodiumhydrocarbonate and 100 ml of ethyl acetate under ice cooling whilestirring, a mixture containing the entire amount (55.6 mmol) ofIntermediate B and 50 ml of ethyl acetate was added dropwise. After thereaction for 30 minutes, the extraction was performed and the organiclayer was washed with water twice and dried over anhydrous magnesiumsulfate. Then, the solvent was distilled off and the crude product waspurified by a silica gel column chromatography (ethylacetate/hexane=1:2) to obtain 19.6 g (43.4 mmol) of Compound A-1 (yield:78.0%).

The compound was identified by NMR and Mass spectra.

¹ H NMR (200 MHz) δ (CDCl₃):

0.90 (3H, t, J=6 Hz), 1.22 (32H, bs), 1.50-1.85 (4H, m), 2.38 (2H, bs),2.45-3.00 (4H, m), 3.32 (3H, bs), 4.10 (2H, t, J=6 Hz), 5.60-5.90 (2H,m), 7.20 (1H, s). ##STR36## SYNTHESIS EXAMPLE 2A: Synthesis of CompoundA-23:

Step 4:

Maleic anhydride (6.2 g (63 mmol)) and 16.2 g (60 mmol) of stearylalcohol were mixed and the mixture was reacted at 120° C. for 2 hours.To the reaction solution, 10 ml of water was added, and the resultingmixture was reacted at 80° C. for 10 minutes, cooled and subjected toliquid separation by adding thereto 100 ml of ethyl acetate and 100 mlof water. The organic layer was washed with water twice, dried overanhydrous magnesium sulfate and distilled off under reduced pressure toobtain 21.8 g of Intermediate C (yield: 98.4%).

Step 5:

To a mixture of 21.8 g (59 mmol) of Intermediate C with 20 ml ofmethylene chloride and 0.5 g of dimethylformamido, 7.9 g (66 mmol) ofthionyl chloride was added dropwise. After reaction at 20° C. for 1hour, the remaining thionyl chloride and methylene chloride weredistilled off under reduced pressure by means of an aspirator to obtainIntermediate D. Intermediate D was used as it was in the next step.

Step 6:

To a mixture of 7.5 g (90 mmol) of N-methylhydroxylamine hydrochloridewith 3.6 g (90 mmol) of sodium hydroxide, 100 ml of water, 15.1 g (180mmol) of sodium hydrocarbon and 100 ml of ethyl acetate under stirringat 15° C., a mixture containing the entire amount of Intermediate D and50 ml of ethyl acetate was added dropwise. After reaction for 30minutes, the reaction mixture was subjected to liquid separation byraising the temperature to 25° C. The organic layer was washed withwater twice, dried over anhydrous magnesium sulfate and distilled offunder reduced pressure. The crude product was purified by a silica gelcolumn chromatography (ethyl acetate/hexane=1:2) to obtain 8.5 g ofCompound A-23 (yield: 36.2%).

The hydroxamic acid compound having a bicyclo ring as a partialstructure for use in the present invention preferably has a bicyclo1,1,1!, 2,1,1!, 2,2,1! or 2,2,2! ring structure as a partial structure.

Among these, those where the bicyclo ring is directed connected to thehydroxyaminocarbonyl group are preferred, and the compound representedby formula (IB) is more preferred.

The compound represented by formula (IB) is described in detail below.

R^(1b) represents a hydrogen atom, a substituted or unsubstituted alkylgroup having from 1 to 30 carbon atoms, a substituted or unsubstitutedcycloalkyl group having from 5 to 30 carbon atoms, a substituted orunsubstituted alkenyl group having from 3 to 30 carbon atoms or asubstituted or unsubstituted cycloalkenyl group having from 5 to 30carbon atoms.

When R^(1b) represents an alkyl group, R^(1b) preferably has a carbonnumber of from 1 to 6. When R^(1b) represents an alkenyl group, R^(1b)preferably has a carbon number of from 3 to 6. Preferred examplesthereof include methyl, ethyl, allyl, n-propyl, isopropyl, n-butyl,sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and prenyl.

Examples of the substituent for the alkyl group or the alkenyl groupinclude an alkyl group, an alkenyl group, an aryl group, a heterocyclicgroup, a halogen atom, an alkoxy group, an aryloxy group, an alkylthiogroup, an arylthio group, a cyano group, a nitro group, analkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyl group, anacyl group, an acyloxy group, an alkylsulfonyl group, an arylsulfonylgroup, an acylamino group, an alkylsulfonamido group and anarylsulfonamido group. Specific examples thereof include 2-chloroethyl,2-methoxyethyl, 2-cyanoethyl, 2-ethoxycarbonylethyl, 3-methylthiopropyl,2-acetylaminoethyl, 3-hydroxypropyl, 2-acetyloxyethyl, 3-chloroethyl,3-methoxyethylallyl and prenyl.

When R^(1b) represents a cycloalkyl group or a cycloalkenyl group,R^(1b) preferably has a carbon atom number of from 5 to 12. Preferredspecific examples thereof include a cyclopentyl group, a cyclohexylgroup, a 1-cyclohexen-1-yl group and 2-cyclohexen-1-yl group.

R^(1b) is preferably an unsubstituted alkyl group having from 1 to 6carbon atoms, more preferably a methyl group or an ethyl group.

R^(2b) represents a substituted or unsubstituted bicycloalkyl grouphaving from 5 to 40 carbon atoms or a substituted or unsubstitutedbicycloalkenyl group having from 5 to 40 carbon atoms.

R^(2b) preferably has a bicyclo 2,2,1!, 2,2,2!, 1,1,1! or 2,1,1! ringstructure.

In the present invention, the bicycloalkyl group means a monovalentgroup obtained by removing one hydrogen of an aliphatic saturatedhydrocarbon, namely, bicycloalkane, constituted only by two ringscovalently having two or more atoms. The bicycloalkenyl group means amonovalent group obtained by removing one hydrogen of an aliphaticunsaturated hydrocarbon, namely, bicycloalkene, constituted only by tworings having at least one double bond and covalently having two or moreatoms.

Among the compounds represented by formula (IB), preferred are thoserepresented by formulae (IIB) and (IIIB).

In formulae (IIB) and (IIIB), R^(1b) represents a hydrogen atom, asubstituted or unsubstituted alkyl group having from 1 to 30 carbonatoms, a substituted or unsubstituted cycloalkyl group having from 5 to30 carbon atoms, a substituted or unsubstituted alkenyl group havingfrom 3 to 30 carbon atoms or a substituted or unsubstituted cycloalkenylgroup having from 5 to 30 carbon atoms;

R^(3b) and R^(4b), which may be the same or different, each represents ahydrogen atom or a substituted or unsubstituted alkyl group having from1 to 30 carbon atoms; and

Q^(1b), Q^(2b) and Q^(3b) each independently represents an atomic groupnecessary for forming a bicyclo ring by combining with the carbon atomsat both terminals.

Specific examples and preferred examples of R^(1b) are the same as thoseof R^(1b) in formula (IB).

When R^(3b) and R^(4b) each represents an alkyl group, R^(3b) and R^(4b)each preferably has a carbon atom number of from 1 to 20, morepreferably from 1 to 8.

Specific examples of R^(3b) and R^(4b) include those described above forR^(1b) in formula (IB).

R^(3b) and R^(4b) each is preferably a hydrogen atom or a methyl group.

Q^(1b), Q^(2b) and Q^(3b) each preferably forms a bicyclo 1,1,1!,2,1,1!, 2,2,1! or 2,2,2! ring structure.

Q^(1b), Q^(2b) and Q^(3b) each more preferably forms a 2,2,1! or 2,2,2!ring.

In formula (IIB), a 2,2,1! ring is preferred.

In formula (IIIB), a 2,2,2! ring is preferred.

In a preferred structure of the compound represented by formula (IIB),R^(1b) is an alkyl group having from 1 to 6 carbon atoms, R^(3b) andR^(4b) each is a hydrogen atom, and Q^(1b), Q^(2b) and Q^(3b) each formsa bicyclo 2,2,1! ring.

In a preferred structure of the compound represented by formula (IIIB),R^(1b) is an alkyl group having from 1 to 6 carbon atoms, R^(3b) is ahydrogen atom or an alkyl group having from 1 to 3 carbon atoms, andQ^(1b), Q^(2b) and Q^(3b) each forms a bicyclo 2,2,2! ring.

A more preferred structure of the compound represented by formula (IB)is the structure represented by formula (VIB): ##STR37## wherein R^(1b)has the same meaning as R^(1b) in formula (IB);

X^(b') represents --OR^(k) or --NR^(k) R^(l) (wherein R^(k) and R^(l),which may be the same or different, each independently represents ahydrogen atom, a substituted or unsubstituted alkyl group having from 1to 30 carbon atoms, a substituted or unsubstituted aryl group havingfrom 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl grouphaving from 2 to 30 carbon atoms or a substituted or unsubstitutedcycloalkyl group having from 5 to 7 carbon atoms, and R^(k) and R^(l)may be combined with each other to form a ring structure); and

R^(a), R^(b), R^(c), R^(d), R^(e), R^(f), R^(g), R^(h), R^(i) and R^(j),which may be the same or different, each independently represents ahydrogen atom or a substituted or unsubstituted alkyl group having from1 to 6 carbon atoms, and R^(c) and R^(f) may be combined to form adouble bond.

Specific examples and preferred examples of R^(1b) are the same as thoseof R^(1b) in formula (IB).

When X^(b') is --OR^(k), R^(k) is preferably a substituted orunsubstituted alkyl group having from 1 to 30 carbon atoms or asubstituted or unsubstituted alkenyl group having from 3 to 30 carbonatoms.

When R^(k) is the alkyl group, the alkyl group may be either branched orlinear.

In this case, examples of the substituent of the alkyl group include analkyl group, a halogen atom, a carboxyl group, an aryl group, a cyanogroup, a sulfamoyl group, an acyl group, a carbamoyl group, analkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, anaryloxycarbonylamino group, a sulfonylamino group, an aminocarbonylaminogroup, a sulfamoylamino group, an amino group, an alkoxy group, anaryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthiogroup, a heterocyclic thio group, a heterocyclic group, an alkylsulfonylgroup or an arylsulfonyl group.

Specific examples of the alkyl group represented by R^(k) are set forthbelow.

In the following chemical formula: ##STR38##

In addition, specific examples include the alkyl groups described abovefor R^(1b). Specific examples of --O--R^(k) further include alkoxygroups derived from a higher alcohol such as Fine Oxocol (trade name,produced by Nissan Chemical KK) 1400, 1600, 1800, 180, 180N, 2000 and2600.

Specific examples of the alkenyl group include allyl homoallyl, prenyland geranyl.

Specific examples of the aryl group include phenyl, 2-naphthyl and2,4-di-t-pentylphenyl.

Examples of the cycloalkyl group represented by R^(k) includecyclohexyl, cyclopentyl and cycloheptyl. Examples of the substituent ofthe cycloalkyl group include an alkoxy group, an alkyl group, anacylamino group, an aminocarbonylamino group, an alkoxycarbonylaminogroup, an aryloxycarbonylamino group, an alkoxycarbonyl group and anaminocarbonyl group.

When X^(b') is --NR^(k) R^(l), R^(k) and R^(l), which may be the same ordifferent, each independently is a hydrogen atom, a substituted orunsubstituted alkyl group having from 1 to 30 carbon atoms, asubstituted or unsubstituted cycloalkyl group having from 5 to 30 carbonatoms, a substituted or unsubstituted aryl group having from 6 to 30carbon atoms or a substituted or unsubstituted alkenyl group having from2 to 30 carbon atoms. The specific examples of the alkyl, aryl,cycloalkyl or alkenyl group include those described above for R^(k).

When X^(b') is --NR^(k) R^(l), R^(k) and R^(l), which may be the same ordifferent, each preferably is a substituted or unsubstituted alkyl grouphaving from 6 to 30 carbon atoms.

Specific examples of R^(a), R^(b), R^(c), R^(d), R^(e), R^(f), R^(g),R^(h), R^(i) and R^(j) include hydrogen, methyl, ethyl, n-propyl,isopropyl, n-butyl, t-butyl, n-hexyl and n-pentyl.

R^(a) and R^(b) are preferably a hydrogen atom at the same time or amethyl group at the same time.

R^(c) and R^(f) are preferably a hydrogen atom at the same time orcombined with each other to form a double bond.

R^(d), R^(e), R^(g), R^(h), R^(i) and R^(j) each is preferably ahydrogen atom.

In a preferred embodiment of formula (VIB), R^(a), R^(b), R^(d), R^(e),R^(g), R^(h), R^(i) and R^(j) are a hydrogen atom at the same time,R^(c) and R^(f) are a hydrogen atom at the same time or are combined toform a double bond, X^(b') is --NR^(k) R^(l), R^(k) and R^(l), which maybe the same or different, each is a substituted or unsubstituted alkylgroup having from 6 to 30 carbon atoms, and R^(1b) is an unsubstitutedalkyl group having from 1 to 6 carbon atoms.

The structure represented by formula (VIB) is more preferablyrepresented by formula (IVB) or (VB): ##STR39## wherein R^(1b) has thesame meaning as R^(1b) in formula (IB);

X^(b) represents --OR^(5b) or --N(R^(5b))(R^(6b)) (wherein R^(5b) andR^(6b), which may be the same or different, each independentlyrepresents a hydrogen atom, a substituted or unsubstituted alkyl grouphaving from 1 to 30 carbon atoms, a substituted or unsubstitutedcycloalkyl group having from 5 to 30 carbon atoms or a substituted orunsubstituted aryl group having from 6 to 30 carbon atoms, and R^(5b)and R^(6b) are combined with each other to form a ring structure);

R^(1b) is preferably an alkyl group having from 1 to 8 carbon atoms, andR^(5b) and R^(6b) each is preferably an alkyl group having from 10 to 22carbon atoms or a substituted or unsubstituted cycloalkyl group havingfrom 5 to 7 carbon atoms.

R^(1b) is more preferably methyl, ethyl, n-propyl or n-hexyl, still morepreferably an alkyl group having from 1 to 6 carbon atoms.

In a preferred embodiment of the formulae, X^(b) is --O--R^(5b) (whereinR^(5b) is a linear alkyl group having a carbon atom number of 14, 16,18, 20 or 22) or --N(R^(5b))(R^(6b)) (wherein R^(5b) and R^(6b) each isa hydrogen atom or a substituted or unsubstituted alkyl group havingfrom 8 to 20 carbon atoms) and R^(1b) is an unsubstituted alkyl grouphaving from 1 to 6 carbon atoms.

In a more preferred embodiment, X^(b) is --N(R^(5b)) (R^(6b)) (whereinR^(5b) and R^(6b) are simultaneously a substituted or unsubstitutedhaving from 8 to 18 carbon atoms) and R^(1b) is a methyl group, an ethylgroup, an n-propyl group or an isopropyl group.

The compound for use in the present invention allows the presence of anantipode and if it is present, the antipode which can be used in thepresent invention may be either an optically active substance or aracemic modification.

Because of the low cost, the racemic modification is preferred.

Specific examples of the present invention are set forth below, however,the present invention is by no means limited thereto.

    ______________________________________                                         ##STR40##                                                                    Compound  R.sup.5b                                                            ______________________________________                                        B-1       C.sub.18 H.sub.37.sup.-n                                            B-2       C.sub.16 H.sub.33.sup.-n                                            B-3       C.sub.14 H.sub.29.sup.-n                                            B-4       C.sub.12 H.sub.25.sup.-n                                            B-5       C.sub.20 H.sub.41.sup.-n                                            B-6       C.sub.22 H.sub.45.sup.-n                                            B-7                                                                                      ##STR41##                                                          B-8                                                                                      ##STR42##                                                          B-9                                                                                      ##STR43##                                                          B-10                                                                                     ##STR44##                                                          B-11                                                                                     ##STR45##                                                          B-12                                                                                     ##STR46##                                                          B-13                                                                                     ##STR47##                                                          B-14                                                                                     ##STR48##                                                          B-15                                                                                     ##STR49##                                                          ______________________________________                                         ##STR50##                                                                    Compound R.sup.5b            R.sup.1b                                         ______________________________________                                        B-16     C.sub.18 H.sub.37.sup.-n                                                                          C.sub.2 H.sub.5                                  B-17     C.sub.16 H.sub.33.sup.-n                                                                          C.sub.3 H.sub.7.sup.-n                           B-18     C.sub.14 H.sub.29.sup.-n                                                                          C.sub.5 H.sub.11.sup.-n                          B-19     C.sub.12 H.sub.25.sup.-n                                                                          C.sub.8 H.sub.17.sup.-n                          B-20     C.sub.10 H.sub.21.sup.-n                                                                          C.sub.12 H.sub.25.sup.-n                         B-21                                                                                    ##STR51##          CH.sub.2 CH.sub.2 OCH.sub.3                      B-22     "                   CH.sub.2 CH.sub.2CN                              B-23                                                                                    ##STR52##          C.sub.3 H.sub.7.sup.-i                           B-24                                                                                    ##STR53##          C.sub.5 H.sub.21.sup.-n                          ______________________________________                                         ##STR54##                                                                    Compound R.sup.5b             R.sup.1b                                        ______________________________________                                        B-25     C.sub.18 H.sub.37.sup.-n                                                                           CH.sub.3                                        B-26     C.sub.16 H.sub.33.sup.-n                                                                           C.sub.2 H.sub.5                                 B-27                                                                                    ##STR55##           C.sub.3 H.sub.7.sup.-n                          B-28                                                                                    ##STR56##           C.sub.5 H.sub.11.sup.-n                         B-29     C.sub.20 H.sub.41.sup.-n                                                                           H                                               B-30     C.sub.14 H.sub.28.sup.-n                                                                            ##STR57##                                      B-31                                                                                    ##STR58##                                                           B-32                                                                                    ##STR59##                                                           B-33                                                                                    ##STR60##                                                           B-34                                                                                    ##STR61##                                                           B-35                                                                                    ##STR62##                                                           B-36                                                                                    ##STR63##                                                           B-37                                                                                    ##STR64##                                                           B-38                                                                                    ##STR65##                                                           B-39                                                                                    ##STR66##                                                           ______________________________________                                         ##STR67##                                                                    Compound X.sup.b              R.sup.1b                                        ______________________________________                                        B-40                                                                                    ##STR68##           CH.sub.3                                        B-41                                                                                    ##STR69##           CH.sub.3                                        B-42                                                                                    ##STR70##           CH.sub.3                                        B-43                                                                                    ##STR71##           CH.sub.3                                        B-44                                                                                    ##STR72##           CH.sub.3                                        B-45                                                                                    ##STR73##           CH.sub.3                                        B-46                                                                                    ##STR74##           C.sub.2 H.sub.5                                 B-47                                                                                    ##STR75##           C.sub.8 H.sub.17.sup.-n                         B-48                                                                                    ##STR76##           C.sub.3 H.sub.7.sup.-n                          B-49                                                                                    ##STR77##           CH.sub.3                                        B-50                                                                                    ##STR78##           C.sub.8 H.sub.17.sup.-n                         ______________________________________                                         ##STR79##                                                                    Com-                                                                          pound X.sup.b                    R.sup.1b                                     ______________________________________                                        B-51                                                                                 ##STR80##                 CH.sub.3                                     B-52                                                                                 ##STR81##                 CH.sub.3                                     B-53  OC.sub.18 H.sub.37.sup.-n  CH.sub.3                                     B-54                                                                                 ##STR82##                 CH.sub.3                                     B-55                                                                                 ##STR83##                 CH.sub.3                                     B-56  OC.sub.18 H.sub.37.sup.-iso                                                                              CH.sub.3                                     B-57                                                                                 ##STR84##                                                              B-58                                                                                 ##STR85##                                                              B-59                                                                                 ##STR86##                                                              B-60                                                                                 ##STR87##                                                              ______________________________________                                    

In the above-described compounds, Compound B-56 was synthesized fromFine Oxocol 180N.

When these compounds allow the presence of an antipode, it is a racemicmodification in all cases, except that in the case of Compound B-39, itis an optically active substance.

The compound represented by formula (IB) has a molecular weight, when itis used to improve storability of a specific layer, of preferably 300 ormore, more preferably 350 or more and most preferably 400 or more.

When the compound for use in the present invention is used only toimprove storability of a specific layer, it should be substantiallyinsoluble in water so that it does not diffuse into the gelatin layer.The term "substantially insoluble in water" as used herein means thatthe solubility at 25° C. in water is 5% or less, preferably 1% or less.

The synthesis method in general of the compound for use in the presentinvention is described below.

The compound for use in the present invention is obtained by condensinga corresponding carboxylic acid chloride with N-alkylhydroxylamine. Thecarboxylic acid chloride can be easily obtained, when the correspondingcarboxylic acid is easily available, by treating the carboxylic acidwith thionyl chloride or oxalyl chloride. In the case of a complexcarboxylic acid, a carboxylic acid is synthesized by a method accordingto respective cases and then treated with thionyl chloride or oxalylchloride. The carboxylic acid can be synthesized in accordance with thefollowing synthesis examples.

On the other hand, with respect to N-alkylhydroxylamine, those where thealkyl is a methyl group are commercially available and others can besynthesized according to the following methods. ##STR88##

Acetone is added to hydroxylamine to convert it into acetoxime and theacetoxime is reacted with an alkylating agent to synthesize N-alkyl form(nitron). Thereafter, acetone is eliminated by performing acid treatmentand as a result, N-alkylhydroxylamine is obtained.

The present invention is described in greater detail by referring to thefollowing synthesis examples of the compound for use in the presentinvention.

SYNTHESIS EXAMPLE 1B:

Synthesis of Compound B-1: ##STR89## Step (1):

To a three-necked flask, 50 g (305 mmol) of Compound a and 82.5 g (305mmol) of stearyl alcohol were added, and they were reacted at 80° C. for6 hours. Thereto, 200 ml of ethyl acetate and 50 ml of acetonitrile wereadded and then allowed to cool to 20° C.

The crystals deposited were collected by filtration, washed by pouring100 ml of acetonitrile thereon and then dried to obtain 105 g ofCompound b (yield: 79.3%).

Step (2):

To a three-necked flask, 30 g (69.0 mmol) of Compound b, 30 ml ofmethylene chloride and 0.1 ml of dimethylformamido were added, andthereto 9.0 g of thionyl chloride was added dropwise while stirring.Thereafter, the mixture was reacted at 40° C. for 1 hour and then,methylene chloride and excessive thionyl chloride were distilled offunder reduced pressure.

The residue obtained was used as it was in the next step.

Step (3):

To a three-necked flask, 100 ml of water, 3.31 g (82.8 mmol) of sodiumhydroxide and 6.92 g (82.8 mmol) of N-methylhyroxylamine hydrochloridewere added and stirred under a nitrogen gas stream and thereto 13.9 g(166 mmol) of sodium hydrocarbon and 100 ml of ethyl acetate was added,followed by cooling to 15° C. To the resulting solution, a solutionhaving dissolved therein the entire amount of Compound b prepared in theprevious step and 100 ml of ethyl acetate was added dropwise.

After the dropwise addition, the mixture was reacted for 30 minutes andsubjected to liquid separation after the temperature thereof was raisedto 50° C. The organic layer was washed with water twice and thencrystallized by adding 100 ml of acetonitrile to the organic layer.

The crystals obtained were collected by filtration, washed withacetonitrile and then dried to obtain 18.1 g (49.5 mmol) of Compound B-1(yield: 71.7%).

NMR Spectrum (300 MHz) δ (CDCl₃):

0.90 (3H, t, J6.8), 1.16-1.42 (30H, m), 1.48 (1H, d, J7.6), 1.55-1.68(2H, m), 3.05 (1H, bs), 3.15 (3H, s), 3.20-3.40 (2H, m), 3.46 (1H, d, d,J₁ 11.4, J₂ 4), 3.70 (1H, d, d, J₁ 11.4, J₂ 4), 3.86-4.09 (2H, m), 6.07(1H, bs), 6.57 (1H, bs), 7.78 (1H, bs).

mp=111°-112° C.

SYNTHESIS EXAMPLE 2B:

Synthesis of Compound B-40: ##STR90## Step (4):

Di-n-octylamine (50.3 g), 100 ml of acetonitrile and 21.1 g oftriethylamine were mixed and thereto a solution having dissolved therein34.2 g of Compound a and 50 ml of acetonitrile was added dropwise underice cooling. The dropwise addition was performed so that the temperatureof the reaction solution could be from 15° to 18° C. The mixture wasreacted for 15 minutes and then subjected to liquid separation by addingthereto water and ethyl acetate. The organic layer was washed with watertwice and dried over magnesium sulfate, and then the solvent wasdistilled off under reduced pressure to obtain Intermediate A.Intermediate A was used as it was in the next step.

Step (5):

Into the entire amount of Intermediate A, 50 ml of methylene chlorideand 0.3 ml of dimethylformamido were added and dissolved, and thereto29.7 g of thionyl chloride was added dropwise at 20° C. After themixture was reacted at 40° C. for 20 minutes, the remaining thionylchloride and methylene chloride were distilled off under reducedpressure by means of an aspirator to obtain Intermediate B. IntermediateB was used as it was in the next step.

Step (6):

Water (250 ml), 10.4 g of sodium hydroxide and 21.7 g ofN-methylhydroxylamine hydrochloride were dissolved at 10° C. under anitrogen gas stream. Then, 43.7 g of sodium hydrocarbon and 300 ml ofethyl acetate were added and thereto a solution obtained by dissolvingthe entire amount of Intermediate B into 100 ml of ethyl acetate wasadded dropwise while keeping the reaction temperature at from 15° to 20°C. The reaction solution was subjected to liquid separation by raisingthe temperature to 50° C. The organic layer was washed with water twiceand dried over magnesium sulfate, and then the solvent was distilled offunder reduced pressure. The residue was crystallized with acetonitrile.The crude crystals obtained were dissolved in 250 ml of hexane and heatfiltered, and after removing the filtrate by distillation under reducedpressure, the residue was recrystallized with a mixed solvent of 50 mlof ethyl acetate, 25 ml of methanol and 250 ml of acetonitrile to obtain30.1 g of Compound B-40 (yield: 33.4%).

300 MHz ¹ H NMR spectrum δ (CDCl₃):

0.90 (3H, t), 0.91 (3H, t), 1.06-1.41 (20H, m), 1.41-1.92 (6H, m),2.82-3.77 (8H, m), 3.16 (3H, s), 5.85-6.20 (1H, m), 6.40-6.68 (1H, m).

SYNTHESIS EXAMPLE 3B:

Synthesis of Compound B-51: ##STR91## Step (7):

Into an autoclave, 50 g of Compound a, 1.0 g of Pd/c (10 wt %) and 400ml of acetic acid were charged, and thereto hydrogen was added at 100°C. at a pressure of 30 kg/cm². After cooling for 4 hours, the reactionsolution was poured into water and crystals deposited were collected byfiltration. The crystals were washed with acetonitrile and dried toobtain 26.2 g of Intermediate C (yield: 51.8%).

Step (8):

Under ice cooling, 20.1 g of di-n-octylamine, 50 ml of acetonitrile and8.4 g of triethylamine were stirred, and thereto a solution obtained bydissolving 14.0 g of Intermediate C into 50 g of acetonitrile was addeddropwise. After the reaction, the reaction solution was subjected toliquid separation by adding ethyl acetate and water. The organic layerwas washed with water twice and dried over magnesium sulfate. Thesolvent was distilled off under reduced pressure and then purified by asilica gel column chromatography (hexane:ethyl acetate=10:1 to 2:1) toobtain 10.5 g of Intermediate D (yield: 45.8%).

Step (9):

Intermediate C (10.0 g), 10 ml of methylene chloride and 0.2 ml ofdimethylformamido were dissolved and thereto 3.5 g of thionyl chloridewas added dropwise at 20° C. while stirring. The mixture was reacted at40° C. for 2 hours and then the remaining thionyl chloride and methylenechloride were distilled of by means of an aspirator to obtainIntermediate E. Intermediate E was used as it was in the next step.

Step (10):

Under a nitrogen gas stream, 50 ml of water, 1.28 g of sodium hydroxideand 2.67 g of N-methylhydroxylamine hydrochloride were dissolved at 10°C. To the resulting solution, 5.38 g of sodium hydrocarbon and 50 ml ofethyl acetate were added and then a 50 ml ethyl acetate solution of theentire amount of Intermediate E was added dropwise while keeping thereaction temperature at from 10° to 15° C. The reaction solution wassubjected to liquid separation after the temperature thereof was raisedto 50° C. The organic layer was washed with water twice and dried overmagnesium sulfate, and then the solvent was distilled off under reducedpressure. The crude product obtained was purified by a silica gel columnchromatography to obtain 8.1 g of Compound B-51 (yield: 58.1%).

300 MHz ¹ H NMR δ (CDCl₃):

0.86 (6H, t), 1.15-1.38 (22H, m), 1.38-1.78 (10H, m), 2.27-2.57 (2H, m),2.57-2.97 (2H, m), 3.07 (3H, s), 3.07-3.47 (2H, m).

Compound B-42 and Compound B-40 were synthesized in the same manner. The300 MHz ¹ H NMR spectrum of Compound B-42 is shown below.

δ (CDCl₃):

1.23-1.58 (2H, m), 1.69-2.09 (5H, m), 3.05-3.32 (5H, m), 3.32-3.62 (5H,m), 6.11-6.42 (2H, m).

The addition amount of the compound for use in the present invention isnot particularly restricted, however, when it is added to alight-sensitive silver halide emulsion layer, it is preferably from1.0×10⁻⁴ to 1.0×10⁻¹ mol, more preferably from 1.0×10⁻³ to 5.0×10⁻² mol,per mol of Ag in the layer to which the compound is added. When thecompound is added to a light-insensitive layer, the addition amount ispreferably from 1×10⁻⁶ to 3×10⁻⁴ mol/m², more preferably from 1×10⁻⁵ to1×10⁻⁴ mol/m².

The compound for use in the present invention may be added afterdissolving it in a water-soluble solvent (e.g., methanol, ethanol,acetone) or after co-emulsifying it with a coupler byemulsion-dispersion. Further, the compound may be previously added atthe preparation of an emulsion. The addition method usingemulsion-dispersion is most preferred.

The layer to which the compound for use in the present invention isadded is not particularly preferred, however, the compound is preferablyadded to a silver halide emulsion layer, more preferably to ared-sensitive layer and/or a green-sensitive layer.

When the present invention is applied to a color photographic material,the color photographic material may suffice if it has at least onelight-sensitive layer on the support. A typical example thereof is asilver halide photographic material comprising a support having thereonat least one light-sensitive layer consisting of a plurality of silverhalide emulsion layers having substantially the same spectralsensitivity but different light sensitivities. The light-sensitive layeris a unit light-sensitive layer having spectral sensitivity to any ofblue light, green light and red light. In the case of a multi-layersilver halide color photographic material, the arrangement of unitlight-sensitive layers are generally such that a red-sensitive unitlayer, a green-sensitive unit layer and a blue-sensitive unit layer areprovided in this order from the support side. However, depending uponthe purpose, the above arrangement order may be reversed or a layerhaving different light sensitivity may be superposed between layershaving the same spectral sensitivity. A light-insensitive layer may beprovided between the above-described silver halide light-sensitivelayers, as an uppermost layer or as the lowermost layer. These layersmay contain a coupler, a DIR compound or a color mixing inhibitor whichwill be described later. Further, these layers may contain a compoundwhich releases imagewise or reverse-imagewise dyes and causes differencein the diffusibility between the dye released and the compound beforethe release.

The silver halide emulsion layers in plurality constituting each unitlight-sensitive layer are preferably arranged such that two layers of ahigh-sensitivity emulsion layer and a low-sensitivity emulsion layer areprovided so that the light sensitivity can be lowered in sequencetowards the support as described in German Patent 1,121,470 and BritishPatent 923,045. Further, it may also be possible to provide alow-sensitivity emulsion layer farther from the support and ahigh-sensitivity emulsion layer nearer to the support as described inJP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543.

Specific examples of the layer arrangement include an order, from thefarthest side to the support, of a low-sensitivity blue-sensitive layer(BL)/a high-sensitivity blue-sensitive layer (BH)/a high-sensitivitygreen-sensitive layer (GH)/a low-sensitivity green-sensitive layer(GL)/a high-sensitivity red-sensitive layer (RH)/a low-sensitivityred-sensitive layer (RL), an order of BH/BL/GL/GH/RH/RL and an order ofBH/BL/GH/GL/RL/RH.

Also, as described in JP-B-55-34932 (the term "JP-B" as used hereinmeans an "examined Japanese patent publication"), a blue-sensitivelayer/GH/RH/GL/RL may be arranged in this order from the farthest sideto the support. Further, as described in JP-A-56-25738 andJP-A-62-63936, a blue-sensitive layer/GL/RL/GH/RH may be arranged inthis order from the farthest side to the support.

An arrangement consisting of three layers different in the lightsensitivity may be used as described in JP-B-49-15495 where a silverhalide emulsion layer having the highest light sensitivity is providedas an upper layer, a silver halide emulsion layer having a lightsensitivity lower than that of the upper layer as a medium layer and asilver halide emulsion layer having a light sensitivity lower than thatof the medium layer as a lower layer so that the light sensitivity canbe lowered in sequence towards the support. Even in the case when such athree layer structure having different light sensitivities is used, asdescribed in JP-A-59-202464, a medium-sensitivity emulsion layer/ahigh-sensitivity emulsion layer/a low-sensitivity emulsion layer may beprovided in this order from the farthest side to the support in thelayer having the same spectral sensitivity.

In addition, an order of a high-sensitivity emulsion layer/alow-sensitivity emulsion layer/a medium-sensitivity emulsion layer or anorder of a low-sensitivity emulsion layer/a medium-sensitivity emulsionlayer/a high-sensitivity emulsion layer may also be used.

In the case of four or more layer structure, the layer arrangement mayalso be changed as described above.

In order to improve color reproducibility, a donor layer (CL) having aspectral sensitivity distribution different from that of mainlight-sensitive layers such as BL, GL and RL and capable of providing aninterlayer effect, is preferably provided adjacent to or in the vicinityof a main light-sensitive layer as described in U.S. Pat. Nos.4,663,271, 4,705,744 and 4,707,436, JP-A-62-160448 and JP-A-63-89850.

The silver halide grain in the photographic emulsion may have a regularcrystal from such as cubic, octahedral or tetradecahedral, an irregularcrystal form such as spherical or platy, a crystal defect such as twin,or a composite form of these.

The silver halide may be a fine grain having a grain size of about 0.2μm or less or a large-sized grain having a grain size in terms of aprojected area diameter up to about 10 μm, and either a polydisperseemulsion or a monodisperse emulsion may be used.

The silver halide photographic emulsion which can be used in the presentinvention can be prepared according to the methods described, forexample, in Research Disclosure (hereinafter referred to as "RD") No.17643, pp. 22-23 "I. Emulsion Preparation and Types" (December, 1978),ibid., No. 18716, p. 648 (November, 1979), ibid., No. 307105, pp.863-865 (November, 1989), P. Glafkides, Chemie et PhisiquePhotographigue, Paul Montel (1967), G. F. Duffin, Photographic EmulsionChemistry, Focal Press (1966), and V. L. Zelikman et al., Making andCoating Photographic Emulsion, Focal Press (1964).

The monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and3,655,394 and British Patent 1,413,748 are also preferably used.

Furthermore, tabular grains having an aspect ratio of about 3 or morecan be used in the present invention. The tabular grain can be easilyprepared by the methods described in Gutoff, Photographic Science andEngineering, Vol. 14, pp. 248-257 (1970), U.S. Pat. Nos. 4,434,226,4,414,310, 4,433,048 and 4,439,520 and British Patent 2,112,157.

The crystal structure may be homogeneous, may comprise a halogencomposition different between the interior and the exterior or may bestratified. A silver halide having a different composition may beconjugated thereto by an epitaxial junction or the silver halide may beconjugated with a compound other than silver halide, such as silverrhodanate or lead oxide. Also,. a mixture of grains having variouscrystal forms may be used.

The above-described emulsion may be a surface latent image-type emulsionforming a latent image mainly on the surface, an internal latentimage-type emulsion forming a latent image inside the grain, or a typeforming a latent image both on the surface of and inside the grain. Theemulsion may be either a negative type emulsion or a positive typeemulsion (so-called autopositive emulsion). When it is a negative typeemulsion, either a normal emulsion or a heat developable emulsion may beused. As one of internal latent image-type emulsions, a core/shellinternal latent image-type emulsion described in JP-A-63-264740 may alsobe used and the preparation method of this emulsion is described inJP-A-59-133542. In this emulsion, the thickness of the shell variesdepending upon the development process and the like, but it ispreferably from 3 to 40 nm, more preferably from 5 to 20 nm.

The silver halide emulsion is usually subjected to physical ripening,chemical ripening and spectral sensitization before use. The additivesused in these steps are described in RD No. 17643, RD No. 18716 and RDNo. 307105 and the pertinent portions thereof are summarized in thetable set forth later.

The photographic material of the present invention may use a mixture oftwo or more kinds of emulsions different at least in one property of thelight-sensitive silver halide emulsion, such as the grain size, thegrain size distribution, the halogen composition, the grain shape or thesensitivity, in the same layer.

It is preferred to apply a silver halide grain of which surface isfogged described in U.S. Pat. No. 4,082,553, a silver halide grain ofwhich inside is fogged described in U.S. Pat. No. 4,626,498 andJP-A-59-214852 or a colloidal silver to a light-sensitive silver halideemulsion layer and/or a substantially light-insensitive hydrophiliccolloid layer. The term "silver halide grain of which inside or surfaceis fogged" as used herein means a silver halide grain which can achieveuniform (non-imagewise) development of a photographic materialirrespective of an unexposed area or an exposed area. The preparationmethod of such a grain is described in U.S. Pat. No. 4,626,498 andJP-A-59-214852. The silver halide forming the inside nucleus of acore/shell type silver halide grain of which inside is fogged may have adifferent halogen composition. The silver halide for the grain of whichinside or surface is fogged may be any of silver chloride, silverbromide, silver iodobromide and silver chloroiodobromide. The foggedsilver halide grain has an average grain size of preferably from 0.01 to0.75 μm, more preferably from 0.05 to 0.6 μm. The grain may have aregular form or may be a polydisperse emulsion, but it is preferablymonodisperse (namely, at least 95% by weight or by number of silverhalide grains having a grain size within an average grain size ±40%).

In the present invention, a light-insensitive fine grain silver halideis preferably used. The term "light-insensitive fine grain silverhalide" as used herein means a silver halide fine grain which is notsensitive to light at the imagewise exposure for obtaining a dye imageand substantially not developed at the development process. Thelight-insensitive fine grain silver halide is preferably not foggedpreviously. The fine grain silver halide has a silver bromide content offrom 0 to 100 mol % and may contain, if desired, silver chloride and/orsilver iodide. It preferably contains from 0.5 to 10 mol % of silveriodide. The fine grain silver halide has an average grain size (anaverage of circle-corresponding diameters of the projected area) ofpreferably from 0.01 to 0.5 μm, more preferably from 0.02 to 0.2 μm.

The fine grain silver halide can be prepared by the same method as thatfor the normal light-sensitive silver halide. The surface of the silverhalide grain needs not be optically sensitized nor be spectrallysensitized. However, it is preferred to add a known stabilizer such as atriazole-base compound, an azaindene-base compound, abenzothiazolium-base compound, a mercapto-base compound or a zinccompound, to the fine grain silver halide in advance of the addition toa coating solution. A layer containing the fine grain silver halidegrain may contain colloidal silver.

The photographic material of the present invention has a coated silveramount of preferably 6.0 g/m² or less, most preferably 4.5 g/m² or less.

The photographic additives which can be used in the present inventionare also described in RDs and the portions having description thereonare shown in the table below.

    ______________________________________                                        Kinds of Additives                                                                           RD17643  RD18716    RD307105                                   ______________________________________                                        1.  Chemical sensitizer                                                                          p. 23    p. 648, right                                                                          p. 866                                                               col.                                              2.  Sensitivity increasing  p. 648, right                                         agent                   col.                                              3.  Spectral sensitizer,                                                                         pp. 23-24                                                                              p. 648, right                                                                          pp. 866-868                                  supersensitizer         col.-p. 649,                                                                  right col.                                        4.  Whitening agent                                                                              p. 24    p. 647, right                                                                          p. 868                                                               col.                                              5.  Light absorbent,                                                                             pp. 25-26                                                                              p. 649, right                                                                          p. 873                                       filter dye,             col.-p. 650,                                          UV absorbent            left col.                                         6.  Binder         p. 26    p. 651, left                                                                           pp. 873-874                                                          col.                                              7.  Plasticizer,   p. 27    p. 650, right                                                                          p. 876                                       lubricant               col.                                              8.  Coating aid,   pp. 26-27                                                                              p. 650, right                                                                          pp. 875-876                                  surface active          col.                                                  agent                                                                     9.  Antistatic agent                                                                             p. 27    p. 650, right                                                                          pp. 876-877                                                          col.                                              10. Matting agent                    pp. 878-879                              ______________________________________                                    

Various dye-forming couplers can be used in the photographic material ofthe present invention and the following couplers are particularlypreferred.

Yellow Coupler:

Couplers represented by formula (I) or (II) of EP-A-502424; couplersrepresented by formula (1) or (2) (particularly, Y-28 at page 18) ofEP-A-513496; couplers represented by formula (I) in claim 1 ofJP-A-5-307248; couplers represented by formula (I) in column 1, lines 45to 55 of U.S. Pat. No. 5,066,576; couplers represented by formula (I) inparagraph 0008 of JP-A-4-274425; couplers (particularly, D-35 at page18) described in claim 1 at page 40 of EP-A-498381; couplers representedby formula (Y) at page 4 (particularly, Y-1 (page 17) and Y-54 (page41)) of EP-A-447969; couplers represented by any one of formulae (II) to(IV) in column 7, lines 36 to 58 (particularly, II-17, II-19 (column 17)and II-24 (column 19)) of U.S. Pat. No. 4,476,219.

Magenta Coupler:

L-57 (page 11, right lower column), L-68 (page 12, right lower column)and L-77 (page 13, right lower column) of JP-A-3-39737; A-4-63 (page134), A-4-73 and A-4-75 (page 139) of EP 456257; M-4, M-6 (page 26) andM-7 (page 27) of EP 486965; M-45 in paragraph 0024 of JP-A-6-43611; M-1in paragraph 0036 of JP-A-5-204106; M-22 in paragraph 0237 ofJP-A-4-362631.

Cyan Coupler:

CX-1, CX-3, CX-4, CX-5, CX-11, CX-12, CX-14 and CX-15 (pages 14 to 16)of JP-A-4-204843; C-7, C-10 (page 35), C-34, C-35 (page 37), (I-1) and(I-17) (pages 42 and 43) of JP-A-4-43345; couplers represented byformula (Ia) or (Ib) in claim 1 of JP-A-6-67385.

Polymer Coupler:

P-1 and P-5 (page 11) of JP-A-2-44345.

As the coupler which provides a colored dye having an appropriatediffusibility, those described in U.S. Pat. No. 4,366,237, BritishPatent 2,125,570, EP-B-96873 and German Patent 3,234,533 are preferred.

As the coupler for correcting unnecessary absorption of a colored dye,yellow colored cyan couplers represented by formula (CI), (CII), (CIII)or (CIV) described at page 5 of EP-A-456257 (particularly, YC-86 at page84); Yellow Colored Magenta Couplers ExM-7 (page 202), EX-1 (page 249)and EX-7 (page 251) described in EP-A-456257; Magenta Colored CyanCouplers CC-9 (column 8) and CC-13 (column 10) described in U.S. Pat.No. 4,833,069; and colorless masking couplers represented by formula (2)(column 8) of U.S. Pat. No. 4,837,136 and formula (A) in claim 1 ofWO92/11575 (particularly, compounds described in pages 36 to 45) arepreferred.

Compounds (including couplers) which release a photographically usefulcompound residue upon reaction with an oxidation product of a developingagent are described below.

Development Inhibitor-Releasing Compound:

Compounds represented by formula (I), (II), (III) or (IV) described atpage 11 of EP-A-378236 (particularly, T-101 (page 30), T-104 (page 31),T-113 (page 36), T-131 (page 45), T-144 (page 51) and T-158 (page 58));compounds represented by formula (I) described at page 7 of EP-A-436938(particularly, D-49 (page 51)); compounds represented by formula (1) ofJP-A-5-307248 (particularly, (23) in paragraph 0027); and compoundsrepresented by formula (I), (II) or (III) described at pages 5 and 6 ofEP-A-440195 (particularly, I-(1) at page 29);

Bleaching Accelerator-Releasing Compound:

Compounds represented by formula (I) or (I') at page 5 of EP-A-310125(particularly (60) and (61) at page 61); and compounds represented byformula (I) in claim 1 of JP-A-6-59411 (particularly, (7) in paragraph0022);

Ligand-Releasing Compound:

Compounds represented by LIG-X described in claim 1 of U.S. Pat. No.4,555,478 (particularly, compounds in column 12, lines 21 to 41);

Leuco Dye-Releasing Compound:

Compounds 1 to 6 in columns 3 to 8 of U.S. Pat. No. 4,749,641;

Fluorescent Dye-Releasing Compound:

Compounds represented by COUP-DYE in claim 1 of U.S. Pat. No. 4,774,181(particularly, compounds 1 to 11 in columns 7 to 10);

Development Accelerator- or Fogging Agent-Releasing Compound:

Compounds represented by formula (1), (2) or (3) in column 3 of U.S.Pat. No. 4,656,123 (particularly (I-22) in column 25) and ExZK-2 at page75, lines 36 to 38 of EP-A-450637;

Compound Which Releases Group Capable of Becoming Dye First WhenReleased:

Compounds represented by formula (I) in claim 1 of U.S. Pat. No.4,857,447 (particularly, Y-1 to Y-19 in columns 25 to 36).

Preferred additives other than couplers are described below.

Dispersion Medium of Oil-Soluble Organic Compound:

P-3, P-5, P-16, P-19, P-25, P-30, P-42, P-49, P-54, P-55, P-66, P-81,P-85, P-86 and P-93 of JP-A-62-215272 (pages 140 to 144);

Latex for Impregnation of Oil-Soluble Organic Compound:

Latexes described in U.S. Pat. No. 4,199,363;

Developing Agent Oxidation Product Scavenger:

Compounds represented by formula (I) in column 2, lines 54 to 62 of U.S.Pat. No. 4,978,606 (particularly, I-(l), I-(2), I-(6) and I-(12)(columns 4 to 5)) and compounds represented by any one of formulae incolumn 2, lines 5 to 10 of U.S. Pat. No. 4,923,787 (particularly,Compound 1 (column 3));

Stain Inhibitor:

Compounds represented by formula (I), (II) or (III) at page 4, lines 30to 33 of EP-A-298321 (particularly, I-47, I-72, III-1 and III-27 (pages24 to 48));

Discoloration Inhibitor:

A-6, A-7, A-20, A-21, A-23, A-24, A-25, A-26, A-30, A-37, A-40, A-42,A-48, A-63, A-90, A-92, A-94 and A-164 of EP-A-298321 (pages 69 to 118),II-1 to III-23 in columns 25 to 38 of U.S. Pat. No. 5,122,444(particularly, III-10), I-1 to III-4 at pages 8 to 12 of EP-A-471347(particularly, II-2) and A-1 to A-48 in columns 32 to 40 of U.S. Pat.No. 5,139,931 (particularly, A-39 and A-42);

Material Which Reduces Use Amount of Coloration Reinforcing Agent orColor Mixing Inhibitor:

I-1 to II-15 at pages 5 to 24 of EP-A-411324 (particularly, I-46);

Formalin Scavenger:

SCV-1 to SCV-28 at pages 24 to 29 of EP-A-477932 (particularly SCV-8);

Hardening Agent:

H-1, H-4, H-6, H-8 and H-14 at page 17 of JP-A-1-214845, compounds (H-1to H-54) represented by any one of formulae (VII) to (XII) in columns 13to 23 of U.S. Pat. No. 4,618,573, Compounds (H-1 to H-76) represented byformula (6) at page 8, right lower column of JP-A-2-214852(particularly, H-14) and compounds described in claim 1 of U.S. Pat. No.3,325,287;

Development Inhibitor Precursor:

P-24, P-37 and P-39 of JP-A-62-168139 (pages 6 to 7) and compoundsdescribed in claim 1 of U.S. Pat. No. 5,019,492 (particularly, 28 and 29in column 7);

Antiseptic, Antimold:

I-1 to III-43 in columns 3 to 15 of U.S. Pat. No. 4,923,790(particularly, II-1, II-9, II-10, II-18 and III-25);

Stabilizer, Antifoggant:

I-1 to I-(14) in columns 6 to 16 of U.S. Pat. No. 4,923,793(particularly, I-1, I-60, I-(2) and I-(13)) and compounds 1 to 65 incolumns 25 to 32 of U.S. Pat. No. 4,952,483 (particularly, 36);

Chemical Sensitizer:

triphenylphosphine, selenide and compound 50 of JP-A-5-40324;

Dye:

a-1 to b-20 at pages 15 to 18 (particularly, a-1, a-12, a-18, a-27,a-35, a-36 and b-5) and V-1 to V-23 at pages 27 to 29 (particularly,V-1) of JP-A-3-156450, F-I-1 to F-II-43 at pages 33 to 55 of EP-A-445627(particularly, F-I-11 and F-II-8), III-1 to III-36 at pages 17 to 28(particularly, III-1 and III-3) of EP-A-457153, fine crystal dispersionproducts of Dye-1 to Dye-124 at pages 8 to 26 of WO88/04794, compounds 1to 22 at pages 6 to 11 of EP-A-319999 (particularly, Compound 1),compounds D-1 to D-87 (pages 3 to 28) represented by formula (1), (2) or(3) of EP-A-519306, compounds 1 to 22 (columns 3 to 10) represented byformula (I) of U.S. Pat. No. 4,268,622 and compounds (1) to (31)(columns 2 to 9) represented by formula (I) of U.S. Pat. No. 4,923,788;

UV Absorbent:

Compounds (18b) to (18r) and 101 to 427 (pages 6 to 9) represented byformula (1) of JP-A-46-3335, compounds (3) to (66) (pages 10 to 44)represented by formula (I) and compounds HBT-1 to HBT-10 (page 14)represented by formula (III) of EP-A-520938, and compounds (1) to (31)(columns 2 to 9) represented by formula (1) of EP-A-521823.

The present invention can be applied to various color photographicmaterials such as color negative film for general use or for movie,color reversal film for slide or for television, color paper, colorpositive film and color reversal paper. Further, the present inventionis suitably used for a film unit with a lens described in JP-B-2-32615and JP-B-U-3-39784 (the term "JP-B-U" as used herein means an "examinedJapanese utility model publication). Furthermore, The present inventioncan be applied to a diffusion transfer type color photograph using heatdevelopment, a diffusion transfer photograph using an autopositiveemulsion or a wet reversal color copying material using an autopositiveemulsion.

Examples of the support properly used in the present invention aredescribed in RD No. 17643, page 28, ibid., No. 18716, from page 647,right column to page 648, left column and ibid., No. 307105, page 879.

In the photographic material of the present invention, the totalthickness of all hydrophilic colloid layers on the side having emulsionlayers is preferably 28 μm or less, more preferably 23 μm or less, stillmore preferably 18 μm or less and most preferably 16 μm or less. Thefilm swelling speed T_(1/2) is preferably 30 seconds or less, morepreferably 20 seconds or less. T_(1/2) is defined as the time requiredfor the film thickness to reach a half (1/2) of a saturation filmthickness which corresponds to 90% of the maximum swollen thicknessachieved at the processing with a color developer at 30° C. for 3minutes and 15 seconds. The film thickness means a film thicknessdetermined at 25° C. and 55% RH (relative humidity) under humidityconditioning for 2 days. T_(1/2) can be measured by means of aswellometer described in A. Green et al, Photogr. Sci. Eng., Vol. 19, 2,pp. 124-129. The T_(1/2) can be adjusted by adding a hardening agent togelatin as a binder or changing the aging conditions after coating. Theswelling rate is preferably from 150 to 400%. The swelling rate can beobtained from the maximum swollen film thickness under theabove-described conditions according to the formula: (maximum swollenfilm thickness--film thickness)/film thickness.

In the photographic material of the present invention, on the sideopposite to the side having emulsion layers, a hydrophilic colloid layer(called back layer) having a total dry thickness of from 2 to 20 μm ispreferably provided. This back layer preferably contains a lightabsorbent, a filter dye, an ultraviolet absorbent, an antistatic agent,a hardening agent, a binder, a plasticizer, a lubricant, a coating agentor a surface active agent, which are described above. The back layer hasa swelling rate of preferably from 150 to 500%.

The photographic material of the present invention can be developedaccording to usual methods described in RD No. 17643, pp. 28-29, ibid.,No. 18716, p. 651, from left to right columns and ibid., No. 307105, pp.880-881.

The color developer used in development of the photographic material ofthe present invention is preferably an alkaline aqueous solutioncomprising as a main component an aromatic primary amine colordeveloping agent. As the color developing agent, an aminophenol-basecompound may be useful but a p-phenylenediamine-base compound ispreferably used and representative and preferred examples thereofinclude compounds described in EP-A-556700, page 28, lines 43 to 52.These compounds may be used in combination of two or more depending onthe purpose.

The color developer usually contains a pH buffer such as a carbonate, aborate or a phosphate of an alkali metal, or a development inhibitor oran antifoggant such as a chloride salt, a bromide salt, an iodide salt,a benzimidazole, a benzothiazole or a mercapto compound. The colordeveloper may also contain, if desired, a preservative such ashydroxylamine, diethylhydroxylamine, sulfite, hydrazines (e.g.,N,N-biscarboxymethylhydrazine), phenylsemicarbazides, triethanolamineand catecholsulfonic acids; an organic solvent such as ethylene glycoland diethylene glycol; a development accelerator such as benzyl alcohol,polyethylene glycol, a quaternary ammonium salt and amines; adye-forming coupler; a competing coupler; an auxiliary developing agentsuch as 1-phenyl-3-pyrazolidone; a tackifying agent; and variouschelating agents including aminopolycarboxylic acid, aminopolyphosphonicacid, alkylphosphonic acid and phosphonocarboxylic acid, such asethylenediaminetetraacetic acid, nitrilotriacetic acid,diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonicacid, nitrilo-N,N,N-trimethylenephosphonic acid,ethylenediamine-N,N,N,N-tetramethylenephosphonic acid,ethylenediamine-di(o-hydroxyphenylacetic acid) and a salt thereof.

In carrying out reversal processing, the color development usuallyfollows black-and-white development. The black-and-white developer usesknown black-and-white developing agents such as dihydoxybenzenes (e.g.,hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone) andaminophenols (e.g., N-methyl-p-aminophenols), individually or incombination. The color developer or the black-and-white developerusually has a pH of from 9 to 12. The replenishing amount of thesedevelopers is, although it may vary depending on the color photographicmaterial to be processed, generally 3 l or less per m² of thephotographic material and when the bromide ion concentration of thereplenisher is lowered, the replenishing amount may be reduced even to500 ml or less. When the replenishing amount is reduced, the contactarea of the processing tank with air is preferably reduced to preventevaporation or air oxidation of the solution.

The processing effect resulting from contact of the photographicprocessing solution with air in a processing tank can be evaluated by anopening ratio (= contact area of the processing solution with air(cm²)!÷ volume of the processing solution (cm³)!. The opening ratio asdefined above is preferably 0.1 or less, more preferably from 0.001 to0.05. The opening ratio can be reduced, for example, by providing ashielding material such as a floating lid on the surface of thephotographic processing solution in the processing tank, by using amovable lid described in JP-A-1-82033 or by a slit development methoddescribed in JP-A-63-216050. The opening ratio is preferably reduced notonly in the color development and black-and-white development but alsoin any subsequent step such as bleaching, bleach-fixing, fixing, waterwashing or stabilization. Further, by using a means for suppressing theaccumulation of bromide ions in the developer, the replenishing amountcan be reduced.

The color development time is usually set to from 2 to 5 minutes,however, further reduction in the processing time can be achieved bycarrying out the processing at a high temperature and a high pH and byusing a color developing agent in a high concentration.

After color development, the photographic emulsion layer is usuallysubjected to bleaching. The bleaching may be conducted at the same timewith the fixing (bleach-fixing) or may be conducted separately. For thepurpose of rapid processing, the bleaching may be followed bybleach-fixing. Further, a processing in a bleach-fixing bath consistingof two continuous tanks, a processing comprising fixing beforebleach-fixing or a processing comprising bleaching after bleach-fixingmay be freely selected depending upon the purpose. Examples of thebleaching agent include compounds of a polyvalent metal such asiron(III), peracids, quinones and nitro compounds. Representativeexamples of the bleaching agent include organic complex salts ofiron(III), for example, complex salts with an aminopolycarboxylic acidsuch as ethylenediaminetetraacetic acid, diethylenetriaminepentaaceticacid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid or glycol ether diaminetetraaceticacid, and complex salts with citric acid, tartaric acid or malic acid.Among these, an aminopolycarboxylic acid ferrate complex salt includingan ethylenediaminetetraacetato ferrate complex salt and1,3-diaminopropanetetraacetato ferrate complex salt is preferred in viewof rapid processing and prevention of environmental pollution. Further,the aminopolycarboxylic acid ferrate complex salt is particularly usefulfor the bleaching solution or for bleach-fixing solution. The bleachingsolution or the bleach-fixing solution using the aminopolycarboxylicacid ferrate complex salt has a pH of generally from 4.0 to 8 but theprocessing may be carried out at a lower pH for expediting theprocessing.

A bleaching accelerator may be used, if desired, in the bleachingsolution, the bleach-fixing solution or a prebath thereof. Specificexamples of useful bleaching accelerators include compounds described inthe following specifications: for example, compounds having a mercaptogroup or a disulfide group described in U.S. Pat. No. 3,893,858, GermanPatent Nos. 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831,JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631,JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426 and RD No.17129 (July, 1978); thiazolidine derivatives described inJP-A-50-140129; thiourea derivatives described in JP-B-45-8506,JP-A-52-20832, JP-A-53-32735 and U.S. Pat. No. 3,706,561; iodide saltsdescribed in German Patent 1,127,715 and JP-A-58-16235; polyoxyethylenecompounds described in German Patent Nos. 966,410 and 2,748,430;polyamine compounds described in JP-B-45-8836; compounds described inJP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727,JP-A-55-26506 and JP-A-58-163940; and bromide ion. Among these,compounds having a mercapto group or a disulfide group are preferred inview of a large acceleration effect and in particular, compoundsdescribed in U.S. Pat. No. 3,893,858, German Patent No. 1,290,812 andJP-A-53-95630 are preferred. Also, compounds described in U.S. Pat. No.4,552,834 are preferred. The bleaching accelerator may be incorporatedinto the photographic material. The bleaching accelerator isparticularly effective in bleach-fixing a color photographic materialfor photographing.

In addition to the above-described compounds, the bleaching solution orthe bleach-fixing solution preferably contains an organic acid in orderto prevent bleaching stains. A particularly preferred organic acid iscompounds having an acid dissociation constant (pKa) of from 2 to 5 andspecific examples thereof include acetic acid, propionic acid andhydroxyacetic acid.

Examples of the fixing agent for use in the fixing solution or thebleach-fixing solution include thiosulfates, thiocyanates,thioether-base compounds, thioureas and a large quantity of iodides.Among these, the thiosulfate is commonly used and an ammoniumthiosulfate can be most widely used. Also, a combination use of athiosulfate with a thiocyanate, a thioether-base compound or a thioureais preferred. As the preservative for the fixing solution or thebleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adductsand sulfinic acid compounds described in EP-A-294769 are preferred.Further, the fixing solution or the bleach-fixing solution preferablycontains various aminopolycarboxylic acids or organic phosphonic acidsfor the purpose of stabilization of the solution.

In the present invention, in order to adjust the pH, a compound having apKa of from 6.0 to 9.0, preferably, an imidazole such as imidazole,1-methylimidazole, 1-ethylimidazole and 2-methylimidazole is preferablyadded to the fixing solution or the bleach-fixing solution in an amountof from 0.1 to 10 mol/liter.

The total desilvering time is preferably as short as possible ifdesilvering failure is not caused. The time is preferably from 1 to 3minutes, more preferably from 1 to 2 minutes. The processing temperatureis from 25° to 50° C., preferably from 35° to 45° C. In this preferredtemperature range, the desilvering rate is improved and the occurrenceof stains after processing can be effectively prevented.

In the desilverization, the stirring is preferably intensified as highlyas possible. Specific examples of the method for intensifying stirringinclude a method of colliding a jet stream of a processing solutionagainst the emulsion surface of the photographic material described inJP-A-62-183460, a method of increasing the stirring effect using arotary means described in JP-A-62-183461, a method of increasing thestirring effect by moving the photographic material while putting theemulsion surface into contact with a wire blade provided in the solutionto cause turbulence on the emulsion surface, and a method of increasingthe circulation flow rate of the entire processing solutions. Such ameans for intensifying the stirring is effective in any of the bleachingsolution, the bleach-fixing solution and the fixing solution. Theintensification of stirring is considered to increase the supply rate ofthe bleaching agent or the fixing agent into the emulsion layer and as aresult, to elevate the desilverization rate. The above-described meansfor intensifying stirring is more effective when a bleaching acceleratoris used and in this case, the acceleration effect can be outstandinglyincreased or the fixing inhibitory action by the bleaching acceleratorcan be eliminated.

The automatic developing machine used for the photographic material ofthe present invention preferably has a transportation means of aphotographic material described in JP-A-60-191257, JP-A-60-191258 andJP-A-60-191259. As described in JP-A-60-191257 above, the transportationmeans can achieve extreme decrease in the amount of a processingsolution carried over from a previous bath to a post bath, provide agreat effect in preventing the deterioration in capacity of theprocessing solution and be particularly effective in reducing theprocessing time or decreasing the replenishing amount of a processingsolution in each step.

The photographic material of the present invention is generallysubjected to water washing and/or stabilization after desilvering. Theamount of water in water washing can be set over a wide range accordingto the characteristics (e.g., due to the material used such as acoupler) or the use of the photographic material and in addition, thetemperature of washing water, the number of water washing tanks (stagenumber), the replenishing system such as countercurrent and cocurrent orother various conditions. Among these, the relation between the numberof water washing tanks and the amount of water in a multi-stagecountercurrent system can be obtained according to the method describedin Journal of the Society of Motion Picture and Television Engineers,Vol. 64, pp. 248-253 (May, 1955). According to the multi-stagecountercurrent system described in the above-described publication, theamount of washing water may be greatly reduced but due to the increasein the residence time of water in the tank, a problem is caused suchthat bacteria proliferate and the floats generated adhere to thephotographic material. In order to solve such a problem, a method ofreducing calcium ions or magnesium ions described in JP-A-62-288838 canbe very effectively used. Further, isothiazolone compounds andthiabendazoles described in JP-A-57-8542, chlorine-base bactericidessuch as sodium chlorinated isocyanurate, benzotriazoles and bactericidesdescribed in Hiroshi Horiguchi, Bokin, Bobai-Zai no Kagaku, SankyoShuppan (1986), Biseibutsu no Mekkin, Sakkin, Bobai-Gijutsu compiled byEisei Gijutsu Kai, issued by Kogyo Gijutsu Kai (1982), and Bokin-BobaiZai Jiten compiled by Nippon Bokin Bobai Gakkai (1986) can be also used.

The washing water in the processing of the photographic material of thepresent invention has a pH of from 4 to 9, preferably from 5 to 8. Thetemperature and the processing time of water washing may be setvariously according to the characteristics and use of the photographicmaterial, but they are commonly from 15° to 45° C. and from 20 secondsto 10 minutes, preferably from 25° to 40° C. and from 30 seconds to 5minutes, respectively. The photographic material of the presentinvention can be processed directly with a stabilizing solution in placeof the above-described water washing. In such a stabilizationprocessing, any known methods described in JP-A-57-8543, JP-A-58-14834and JP-A-60-220345 can be used.

In some cases, the stabilization processing may be further carried outafter the above-described water washing. An example thereof is astabilization bath containing a dye stabilizing agent and a surfaceactive agent used as a final bath of a color photographic material forphotographing. Examples of the dye stabilizing agent include aldehydessuch as formalin and glutaraldehyde, N-methylol compounds andhexamethylenetetramine or aldehyde sulfite addition products.

This stabilization bath may also contain various chelating agents andantimolds.

The overflow solution accompanying the replenishing of theabove-described washing water and/or stabilization solution can bere-used in other processing steps such as desilvering.

In the processing, for example, using an automatic developing machine,if the above-described respective processing solutions are concentrateddue to evaporation, water is preferably added to correct theconcentration.

A color developing agent may be incorporated into the photographicmaterial of the present invention so as to simplify and expedite theprocessing. The color developing agent is preferably incorporated intothe photographic material as a block compound thereof. Examples of theblock compound include indoaniline compounds described in U.S. Pat. No.3,342,597, Schiff base-type compounds described in U.S. Pat. No.3,342,599, Research Disclosure No. 14850 and ibid., No. 15159, aldolcompounds described in ibid., No. 13924, metal salt complexes describedin U.S. Pat. No. 3,719,492 and urethane-based compounds described inJP-A-53-135628.

The photographic material of the present invention may contain, ifdesired, various 1-phenyl-3-pyrazolidones for the purpose ofaccelerating the color development. Typical examples of the compound aredescribed in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

Each processing solution used for processing the photographic materialof the present invention is used at a temperature of from 10° to 50° C.Usually, the temperature as a standard is from 33° to 38° C. but highertemperatures may be used to accelerate the processing to thereby shortenthe processing time or on the contrary, lower temperatures may be usedto achieve improved image quality or improved stability of theprocessing solution.

There is no particular restriction on various additives and developmentprocessing used when the present invention is applied to ablack-and-white photographic material and, for example, those describedin JP-A-2-68539, JP-A-5-11389 and JP-A-2-58041 can be preferably used,of which pertinent portions are described below.

1. Silver halide emulsion and production process thereof:

JP-A-2-68539, from page 8, right lower column, line 6 from the bottom topage 10, right upper column, line 12

2. Chemical sensitization method:

JP-A-2-68539, page 10, from right upper column, line 13 to left lowercolumn, line 16, and selenium sensitization method described inJP-A-5-11389

3. Antifoggant, stabilizer:

JP-A-2-68539, from page 10, left lower column, line 17 to page 11, leftupper column, line 7 and from page 3, left lower column, line 2 to page4, left lower column

4. Spectral sensitizing dye:

JP-A-2-68539, from page 4, right lower column, line 4 to page 8, rightlower column and JP-A-2-58041, page 12, from left lower column, line 8to right lower column, line 19

5. Surface active agent, antistatic agent:

JP-A-2-68539, from page 11, left upper column, line 14 to page 12, leftupper column, line 9 and JP-A-2-58041, from page 2, left lower column,line 14 to page 5, line 12.

6. Matting agent, plasticizer, slipping agent:

JP-A-2-68539, page 12, from left upper column, line 10 to right uppercolumn, line 10 and JP-A-2-58041, from page 5, left lower column, line13 to page 10, left lower column, line 3

7. Hydrophilic colloid:

JP-A-2-68539, page 12, from right upper column, line 11 to left lowercolumn, line 16

8. Hardening agent:

JP-A-2-68539, from page 12, left lower column, line 17 to page 13, rightupper column, line 6

9. Development processing:

JP-A-2-68539, page 15, from left upper column, line 14 to left lowercolumn, line 13

In addition to those described in the foregoing, the present inventioncan be applied to a diffusion transfer photograph, a so-calledinstantaneous photograph. Examples of the diffusion transfer photographare described in JP-A-5-297544.

Further, the present invention can be used in a heat developablephotographic material. The heat developable photographic material inwhich the present invention can be used may be one which forms ablack-and-white image or one which forms a color image. Examples thereofinclude heat developable photographic materials described inJP-A-60-162251, JP-A-64-13546, JP-A-1-161236, U.S. Pat. Nos. 4,474,867,4,478,927, 4,507,380, 4,500,626, 4,483,914, 4,783,396 and 4,740,445,JP-A-59-231539 and JP-A-60-2950.

Furthermore, the present invention can be used in a wet reversal colorcopying material using an autopositive emulsion. This material isdescribed as Sample 101 in Example 1 of JP-A-3-152530 or as Sample 1 inJP-A-2-90145.

The silver halide photographic material for color diffusion transfer towhich the present invention can be applied, is described below.

The photographic material for use in the present invention fundamentallycomprises light-sensitive silver halide, binder and dye-donatingcompound (which sometimes acts also as a reducing agent) on a support.These components are added to the same layer in many cases, however, ifthey can remain in a reactive state, the components may be divided andadded to separate layers. For example, when a colored dye-donatingcompound is made be present in the lower layer of a silver halideemulsion, the reduction in sensitivity can be prevented.

In order to obtain colors over a wide range within the chromaticitydiagram using three primary colors of yellow, magenta and cyan, at leastthree silver halide emulsion layers having sensitivity in differentspectral regions are used in combination. For example, a three-layercombination of a blue-sensitive layer, a green-sensitive layer and ared-sensitive layer, a combination of a green-sensitive layer, ared-sensitive layer and an infrared-sensitive layer, and a combinationof a red-sensitive layer, a first infrared-sensitive layer and a secondinfrared-sensitive layer may be used. Respective light-sensitive layersmay be arranged in various orders known for usual color photographicmaterials. Further, each light-sensitive layer may be divided into twoor more layers, if desired.

In the heat developable photographic material, various auxiliary layerssuch as a protective layer, an undercoat layer, an interlayer, a yellowfilter layer, an antihalation layer and a back layer may be provided.

(Fundamental Structure and Preparation Method of Silver Halide Grain)

The silver halide which can be used in the present invention may be anyof silver chloride, silver bromide, silver iodobromide, silverchlorobromide, silver iodochloride and silver chloroiodobromide,however, silver iodobromide, silver chloride, silver bromide and silverchlorobromide each having a silver iodide content of about 30 mol % orless are preferred.

The silver halide emulsion for use in the present invention may beeither a surface latent image-type emulsion or an internal latentimage-type emulsion. The internal latent image-type emulsion is used asa direct reversal emulsion in combination with a nucleating agent or alight fogging agent. A so-called multiple structure grain havingdifferent halogen compositions between the inside and the surface of agrain may also be used. Out of multiple structure grains, particularlythose having a double structure are sometimes called a core/shellemulsion.

The silver halide for use in the present invention is preferably amultiple structure grain emulsion, more preferably a core/shellemulsion. However, the present invention is by no means limited thereto.The silver halide emulsion for use in the present invention ispreferably a monodisperse emulsion and the coefficient of variationdescribed in JP-A-3-110555 is preferably 20% or less, more preferably16% or less, still more preferably 10% or less. However, the presentinvention is by no means limited to this monodisperse emulsion.

The silver halide grain to which the present invention can be applied isnot particularly restricted on the average grain size, however, theaverage grain size is preferably from 0.1 to 2.2 μm, more preferablyfrom 0.1 to 1.2 μm. The crystal habit of the silver halide grain may beany of cubic form, octahedral form, tabular form having a high aspectratio and pebble like form. More preferred is a cubic emulsion. To sayspecifically, any of silver halide emulsions described in U.S. Pat. No.4,500,626, column 50, and U.S. Pat. No. 4,628,021, Research Disclosure,No. 17029 (1978), and JP-A-62-25159 can be used.

During preparation of the silver halide emulsion of the presentinvention, a so-called desilvering process is preferably performed toremove salts in excess. The desilvering may be performed by a noodlewater washing method where the desilvering is performed while gellinggelatin, or by a flocculation method using an inorganic salt comprisingpolyvalent anions (e.g., sodium sulfate), an anionic surface activeagent, an anionic polymer (e.g., polystyrenesulfonic acid), or a gelatinderivative (e.g., aliphatic acylated gelatin, aromatic acylated gelatin,aromatic carbamoylated gelatin). Preferably, flocculation using acompound represented by Flocculant (a) or Flocculant (b) which will bedescribed layer, is used, however, the present invention is by no meanslimited thereto. Further, ultrafiltration using no flocculant may beused. The removal of excessive salts may be omitted.

The silver halide emulsions for use in the present invention may containheavy metals, such as iridium, rhodium, platinum, cadmium, zinc,thallium, lead, iron, and chromium, for various purposes. Thesecompounds may be used individually or in combination of two or more ofthem. The addition amount varies depending on the purpose, however, ingeneral, it is approximately from 10⁻⁹ to 10⁻³ mol per mol of silverhalide. The compound may be incorporated uniformly into a grain or maybe locally present in the inside or on the surface of a grain.

The addition amount of iridium for use in the present invention ispreferably from 10⁻⁹ to 10⁻⁴ mol, more preferably from 10⁻⁸ to 10⁻⁶ mol,per mol of silver halide. In the case of a core/shell emulsion, theiridium may be added to the core and/or the shell. Preferred examples ofthe iridium compound include K₂ IrCl₆ and K₃ IrCl₆.

The addition amount of rhodium for use in the present invention ispreferably from 10⁻⁹ to 10⁻⁶ mol per mol of silver halide. The additionamount of iron for use in the present invention is preferably from 10⁻⁷to 10⁻³, more preferably from 10⁻⁶ to 10⁻³ mol, per mol of silverhalide. A method where a part or whole of the above-described heavymetal is previously doped to a fine grain emulsion of silver chloride,silver chlorobromide, silver bromide or silver iodobromide and the finegrain emulsion is added to locally dope the metal onto the silver halideemulsion surface, is also preferably used. At the stage of formingsilver halide grains, rhodanates, NH₃, 4-substituted thioether compoundsrepresented by Compound (a) which will be described later, organicthioether derivatives described in JP-B-47-11386 or sulfur-containingcompounds described in JP-A-53-144319 may be used as a silver halidesolvent.

At the stage of forming silver halide grains, nitrogen-containingcompounds described in JP-B-46-7781, JP-A-60-222842 and JP-A-60-122935may be added.

Gelatin is advantageous as a protective colloid or as a binder of otherhydrophilic colloids used in the preparation of emulsion of the presentinvention, however, a hydrophilic colloid other than gelatin can also beused. Examples thereof include proteins such as gelatin derivatives,graft polymers of gelatin to other polymer, albumin and casein;cellulose derivatives such as hydroxyethyl cellulose and cellulosesulfates; sodium arginates and starch derivatives; and various synthetichydrophilic high polymer materials such as homopolymers and copolymersof polyvinyl alcohol, polyvinyl alcohol partial acetal,poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,polyacrylamido, polyvinyl imidazole and polyvinyl pyrazole.

The gelatin may be a lime-processed gelatin, an acid-processed gelatinor an enzyme-processed gelatin as described in Bull. Soc. Sci. Photo.Japan, No. 16, p. 30 (1966), and a hydrolysate of gelatin or anenzymolysate of gelatin can also be used.

With respect to other conditions, P. Glafkides, Chemie et PhisiguePhotographigue, Paul Montel (1967), G. F. Duffin, Photographic EmulsionChemistry, The Focal Press (1966), and V. L. Zelikman et al., Making andCoating Photographic Emulsion, The Focal Press (1964) may be referredto. More specifically, any of an acid method, a neutral method and anammonia method may be used, and as the system of reacting a solublesilver salt and a soluble halide, any of a single jet method, a doublejet method and a combination of these may be used.

A method of forming grains in the presence of excessive silver ions(so-called reversed mixing method) may also be used. Further, as onesystem of a double jet method, a method of maintaining the pAg in theliquid phase where silver halide is formed constant, a so-calledcontrolled double jet method, may also be used. To accelerate the growthof grains, the concentration, addition amount and addition rate ofsilver salts and halogen salts may be increased (as described inJP-A-55-142329, JP-A-55-158124, and U.S. Pat. No. 3,650,757). Duringgrain formation or after grain formation, the silver halide grainsurface may be substituted by a halogen of forming difficultly solublesilver halide grains.

The stirring of the reaction solution may be performed by any knownstirring method. The temperature and pH of the reaction solution duringformation of silver halide grains may be freely selected, however, thepH is preferably form 2.2 to 6.0, more preferably from 3.0 to 5.5.

The emulsion for a blue-sensitive layer used in the present invention isdescribed in JP-A-5-119429. A silver halide emulsion comprising silverhalide grains having a high silver iodide content layer on the grainsurface and subjected to chemical sensitization before desilvering andaddition of iodine ions is particularly preferred.

(Addition Method of Sensitizing Dye)

The sensitizing dye may be added basically at any time. Morespecifically, the sensitizing dye may be added at the beginning (may beadded before nucleation) of, during or after formation of silver halideemulsion grains, at the beginning of, during or after completion of thedesilvering, during redispersion of gelatin, before, during or after thechemical sensitization or at the preparation of coating solution. Thesensitizing dye is preferably added during or after completion of theformation of silver halide grains, or before, during or after thechemical sensitization. The term "after the chemical sensitization" asused herein means that the sensitizing dye is added after all chemicalsnecessary for the chemical sensitization are added.

As described in U.S. Pat. No. 4,183,756, the sensitizing dye may be madepresent in the reaction system of a soluble silver salt (e.g., silvernitrate) with a halide (e.g., potassium bromide) before silver halidegrains are generated. Further, as described in U.S. Pat. No. 4,225,666,the sensitizing dye may be made present in the above-described reactionsystem after the nucleation of silver halide grains and at the same timebefore completion of the silver halide grain formation. Furthermore, thesensitizing dye may be made present at the same time with the formationof silver halide grains, namely, may be made present in the reactionsolution at the same time with the mixing of a silver salt with ahalide. The photographic material containing the thus-prepared emulsionis more excellent in the storability at high temperatures and in thegradation. The concentration of the solution added, the solvent, theaddition time (either addition at once or addition over a time period),the temperature and the pH may be freely selected. Further, eitherliquid level addition or submerged addition may be used. Theseconditions are described in detail in JP-A-3-110555.

(Kind of Sensitizing Dye)

The dye for use in the emulsion used in the present invention includescyanine dyes, merocyanine dyes, complex cyanine dyes, complexmerocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyesand hemioxonol dyes. Specific examples thereof include sensitizing dyesdescribed in U.S. Pat. No. 4,617,257, JP-A-59-180550, JP-A-60-140335 andRD, No. 17029, pp. 12-13 (1978). These sensitizing dyes may be usedindividually or in combination, and the combination of sensitizing dyesare often used for the purpose of supersensitization. Together with thesensitizing dye, a dye which itself has no spectral sensitizationeffect, or a compound which absorbs substantially no visible light, butexhibits supersensitization may be incorporated into the emulsion (e.g.,those described in U.S. Pat. No. 3,615,641, JP-A-63-23145).

In the present invention, the entire amount of sensitizing dye may beadded at once or the sensitizing dye may be added by severalinstallments even if any of the above-described methods may be used.Further, the sensitizing dye may be added as a mixture with a solublesilver salt and/or a halide.

The sensitizing dye may be added after dissolving it in an organicsolvent having compatibility with water, such as methanol, ethanol,propanol, fluorinated alcohol, methyl cellosolve, dimethylformamido andacetone, or in water (which may be either alkaline or acidic). Further,two or more of those described above may be used in combination.Furthermore, the sensitizing dye may be added in the form of adispersion in a water/gelatin dispersion system or of a freeze-driedpowder. Still further, the sensitizing dye may be added as a powder orsolution where the dye is dispersed using a surface active agent.Examples of the sensitizing dye for use in the emulsion according to thepresent invention also include those described in JP-A-3-296745 andJP-A-4-31854. The use amount of the sensitizing dye is suitably from0.001 to 20 g, preferably from 0.01 to 2 g, per 100 g of silver used inpreparation of the emulsion.

(Chemical Sensitization)

The silver halide emulsion for use in the present invention may be usedin the state of being not chemically sensitized, however, it ispreferably subjected to chemical sensitization to increase sensitivity.The chemical sensitization may be performed using any of sulfursensitization, gold sensitization, reduction sensitization and acombination of these.

In addition, chemical sensitization using a compound containing achalcogen element other than sulfur, such as selenium or tellurium, orchemical sensitization using a noble metal such as palladium or iridium,may also be performed in combination with the above-described chemicalsensitization.

Further, a method of using an inhibitor such as a nitrogen-containingheterocyclic compound including4-hydroxy-6-methyl(1,3,3a,7)tetraazaindene may also be preferably used.The addition amount is preferably from 10⁻⁵ to 10⁻¹ mol per mol ofsilver halide.

The pH at the time of chemical sensitization is preferably from 5.3 to10.5, more preferably from 5.5 to 9.5.

The sulfur sensitizer is a compound containing sulfur capable ofreacting with active gelatin or silver. Examples thereof includethiosulfate, allylthiocarbamido, thiourea, allylisothiacyanate, cystine,p-toluenethiosulfonic acid, rhodanine and mercapto compounds. Inaddition, those described in U.S. Pat. Nos. 1,574,944, 2,410,689,2,278,947, 2,728,668 and 3,656,955 may also be used.

The coating amount of the light-sensitive silver halide used in thepresent invention is from 1 mg/m² to 10 g/m² as calculated in terms ofsilver.

The silver halide emulsion may be used in the state of being notpost-ripened, however, it is usually subjected to chemical sensitizationbefore use. Sulfur sensitization, reduction sensitization, noble metalsensitization and selenium sensitization, which are known for theemulsion used in normal photographic materials, may be used individuallyor in combination. The chemical sensitization may also be performed inthe presence of a nitrogen-containing heterocyclic compound(JP-A-62-253159).

When the present invention is applied to a heat developable photographicmaterial, an organic metal salt may be used as an oxidizing agent incombination with the light-sensitive silver halide. Among the organicmetal salts, an organic silver salt is particularly preferably used.

The organic compound which can be used in forming the above-describedorganic silver salt oxidizing agent, include benzotriazoles described inU.S. Pat. No. 4,500,626, columns 52 to 53, fatty acids and othercompounds. Further, silver salts of carboxylic acid having an alkynylgroup such as silver phenylpropiolate described in JP-A-60-113235 andsilver acetylide described in JP-A-61-249044 are useful. The organicsilver salts may be used in combination of two or more thereof.

The organic silver salt is used in an amount of from 0.01 to 10 mol,preferably from 0.01 to 1 mol, per mol of light-sensitive silver halide.The coating amount in total of the light-sensitive silver halide and theorganic silver salt is suitably from 50 mg/m² to 10 g/m² as calculatedin terms of silver.

In the present invention various antifoggants and photographicstabilizers may be used. Examples thereof include azoles and azaindenesdescribed in RD, No. 17643, pp. 24-25 (1978), nitrogen-containingcarboxylic acids and phosphoric acids described in JP-A-59-168442,mercapto compounds and metal salts thereof described in JP-A-59-111636,and acetylene compounds described in JP-A-62-87957.

The binder in constituent layers of a photographic material or adye-fixing element is preferably hydrophilic. Examples thereof includethose described in JP-A-62-253159, pages (26) to (28). Morespecifically, transparent or translucent hydrophilic binders arepreferred and examples thereof include natural compounds such asproteins (e.g., gelatin, gelatin derivatives) and polysaccharides (e.g.,cellulose derivatives, starch, gum arabic, dextran, pullulane); andsynthetic high polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone and acrylamido polymers. Further, highly water-absorbingpolymers described in JP-A-62-245260, namely, homopolymers of vinylmonomers having --COOM or --SO₃ M (wherein M is a hydrogen atom or analkali metal), or copolymers of the vinyl monomers or of the vinylmonomer with other vinyl monomer (for example, sodium methacrylate,ammonium methacrylate, Sumikagel L-5H produced by Sumitomo ChemicalCompany Limited), may also be used. The above-described binders may beused in combination of two or more thereof.

When a system of performing heat development while supplying a slightamount of water is used, water can be absorbed rapidly by using theabove-described highly water-absorbing polymer. Further, when the highlywater-absorbing polymer is used in a dye-fixing layer or a protectivelayer thereof, the re-transfer of the transferred dye from thedye-fixing element to other members can be prevented.

In the present invention, the coating amount of the binder is preferably20 g/m² or less, more preferably 10 g/m² or less, and still morepreferably 7 g/m² or less.

The constituent layer (including a back layer) of the photographicmaterial or the dye-fixing element may contain various polymer latexesfor the purpose of improving physical properties of the layer such asdimensional stabilization or prevention of curling, adhesion, crackingof layers or reduction/increase in sensitivity due to pressure. Specificexamples of the polymer latex include those described in JP-A-62-245258,JP-A-62-136648 and JP-A-62-110066. In particular, a polymer latex havinga low glass transition point (40° C. or lower) is used in a mordantlayer, cracking of the mordant layer can be prevented, whereas when apolymer latex having a high glass transition point is used in a backlayer, a curl-preventing effect can be provided.

The reducing agent for use in the present invention may be one known inthe field of photographic materials. The reducing agent also includesthe dye-donating compounds having a reducing property which will bedescribed later (in this case, other reducing agent can be used incombination). Further, a reducing agent block compound which itself hasno reducing property but shows the reducing property upon having actionof a nucleophilic reagent or heat during the development, may also beused.

Examples of the reducing agent for use in the present invention includereducing agents and reducing agent block compounds as described in U.S.Pat. No. 4,500,626 (columns 49 and 50), U.S. Pat. No. 4,483,914 (columns30 and 31), U.S. Pat. Nos. 4,330,617 and 4,590,152, JP-A-60-140335(pages (17) and (18)), JP-A-57-40245, JP-A-56-138736, JP-A-59-178458,JP-A-59-53831, JP-A-59-182449, JP-A-59-182450, JP-A-60-119555,JP-A-60-128436 through JP-A-60-128439, JP-A-60-198540, JP-A-60-181742,JP-A-61-259253, JP-A-62-244044, JP-A-62-131253 through JP-A-62-131256,and EP-A-220746 (pages 78 to 96).

Combinations of various reducing agents described in U.S. Pat. No.3,039,869 can also be used.

When a non-diffusible reducing agent is used, an electron-transferringagent and/or an electron-transferring agent block compound may be usedin combination, if desired, so as to accelerate the movement ofelectrons between the non-diffusible reducing agent and the developablesilver halide.

The electron-transferring agent or a block compound thereof may beselected from the above-described reducing agents and block compoundsthereof. The electron-transferring agent or the block compound thereofpreferably has mobility larger than that of the non-diffusible reducingagent (electron-donor). Particularly useful electron-transferring agentsare 1-phenyl-3-pyrazolidones and aminophenols.

The non-diffusible reducing agent (electron-donor) for use incombination with the electron-transferring agent may be selected fromthe above-described reducing agents as long as it does not substantiallymove between layers of the photographic material. Preferred examplesthereof include hydroquinones, sulfonamidophenols, sulfonamidonaphthols,compounds described as the electron-donor in JP-A-53-110827, andnon-diffusible dye-donating compounds having a reducing property whichwill be described later.

The addition amount of the reducing agent is from 0.01 to 20 mol,preferably from 0.1 to 10 mol, per mol of silver.

In the present invention, the photographic material contains a compoundwhich forms or releases a mobile dye in correspondence orcounter-correspondence to the reaction of reducing silver ions to silverunder high temperature conditions, namely, a dye-donating compound.

The dye-donating compound which can be used in the present invention isrepresented by formula (LI):

    (Dye-G).sub.q -Y                                           (LI)

wherein Dye is a dye group, a dye group temporarily shifted to shortwave or a dye precursor group, q represents a positive integer, Grepresents a mere bond or a divalent linking group, and Y represents agroup capable of cleaving the Y-G bond in correspondence orcounter-correspondence with the development of silver halide and causingdifference in the diffusibility between the compound represented byDye-G and the compound represented by (Dye-G)_(q) -Y.

The hydrophobic additives such as dye-donating compounds andnon-diffusible reducing agents may be incorporated into layers of thephotographic material according to known methods described, for example,in U.S. Pat. No. 2,322,027. In this case, a high boiling point organicsolvent as described in JP-A-59-83154, JP-A-59-178451, JP-A-59-178452,JP-A-59-178453, JP-A-59-178454, JP-A-59-178455 and JP-A-59-178457 may beused, if desired, in combination with a low boiling point organicsolvent having a boiling point of from 50° to 160° C.

The use amount of the high boiling point organic solvent is 10 g orless, preferably 5 g or less, per g of the dye-donating compound. Or, itis 1 ml or less, preferably 0.5 ml or less, more preferably 0.3 ml orless, per g of the binder.

A dispersion method using a polymer material described in JP-B-51-39853and JP-A-51-59943 can also be used.

In the case of a substantially water-insoluble compound, a method offorming the compound into fine particles and then dispersing andincorporating them into the binder may be used, other than theabove-described method.

In dispersing a hydrophobic compound in a hydrophilic colloid, varioussurface active agents may be used. Examples thereof include thosedescribed as the surface active agent in JP-A-59-157636, pages (37) to(38).

In the present invention, the photographic material may use a compoundcapable of achieving activation of development and at the same time,stabilization of an image. Preferred specific examples thereof includethose described in U.S. Pat. No. 4,500,626, columns 51 and 52.

The photographic material may contain a non-diffusible filter dye forthe purpose of improving sharpness. If desired, a filter dye havingabsorption in an infrared region may also be used. These filter dyes aredescribed in detail in JP-A-4-31854, JP-A-4-217243, JP-A-4-276744 andJP-A-5-45834.

In a system of forming an image by the diffusion transfer of a dye, adye-fixing element is used in combination with the photographicmaterial. The dye-fixing element and the photographic material may beindependently provided on separate supports or may be provided on thesame support. With respect to the relationship of the photographicmaterial with the dye-fixing element, the relationship with the support,the relationship with the white reflecting layer, the relationshipdescribed in U.S. Pat. No. 4,500,626, column 57, can also be applied tothe present invention.

The dye-fixing element which is preferably used in the present inventionhas at least one layer containing a mordant and a binder. The mordantmay be one known in the photographic field. Specific examples thereofinclude mordants described in U.S. Pat. No. 4,500,626 (columns 58 and59) and JP-A-61-88256 (pages (32) to (41)), and those described inJP-A-62-244043 and JP-A-62-244036. Further, dye-accepting high polymercompounds described in U.S. Pat. No. 4,463,079 may also be used.

In the dye-fixing element, if desired, auxiliary layers such as aprotective layer, a peeling-off layer or a curling-preventive layer maybe provided. It is particularly advantageous to provide a protectivelayer.

The constituent layers of the photographic material or the dye-fixingelement may contain a plasticizer, a slipping agent or a high boilingpoint organic solvent as an improver of releasability between thephotographic material and the dye-fixing element. Specific examplesthereof include those described in JP-A-62-253159 (page (25) ) andJP-A-62-245253. Further, in order to achieve the above-describedpurpose, various silicone oils (including all silicone oils of fromdimethyl silicone oil to modified silicone oils resulting fromintroducing various organic groups into dimethylsiloxane) may be used.Examples thereof include various modified silicone oils described inModified Silicone Oils (Technical Data P6-18B), issued by Shin-EtsuSilicone KK. In particular, a carboxy-modified silicone (trade name:X-22-3710) is effective. Further, silicone oils described inJP-A-62-215953 and JP-A-63-46449 are also effective.

The photographic material and the dye-fixing element may use adiscoloration inhibitor. Examples of the discoloration inhibitor includeantioxidants, ultraviolet absorbents and certain kinds of metalcomplexes.

Examples of the antioxidant include chroman-base compound,coumarane-base compounds, phenol-base compounds (e.g., hinderedphenols), hydroquinone derivatives, hindered amine derivatives andspiroindane-base compounds. Also, the compounds described inJP-A-61-159644 are effective.

Examples of the ultraviolet absorbent include benzotriazole-basecompounds (described, for example, in U.S. Pat. No. 3,533,794),4-thiazolidone-base compounds (described, for example, in U.S. Pat. No.3,352,681), benzophenone-base compounds (described, for example, inJP-A-46-2784) and compounds described in JP-A-54-48535, JP-A-62-136641and JP-A-61-88256. Also, ultraviolet absorbing polymers described inJP-A-62-260152 are effective.

Examples of the metal complex include compounds described in U.S. Pat.Nos. 4,241,155, 4,245,018 (columns 3 to 36) and U.S. Pat. No. 4,254,195(columns 3 to 8), JP-A-62-174741, JP-A-61-88256 (pages (27) to (29)),JP-A-63-199248, JP-A-1-75568 and JP-A-1-74272.

Examples of useful discoloration inhibitors are described inJP-A-62-215272 (pages (125) to (137)).

The discoloration inhibitor which inhibits discoloration of a dyetransferred onto the dye-fixing element, may be previously incorporatedinto the dye-fixing element or may be supplied to the dye-fixing elementfrom the external, for example, from the photographic material.

The above-described antioxidants, ultraviolet absorbents and metalcomplexes may be used in combination of these.

The photographic material or the dye-fixing element may use afluorescent brightening agent. It is particularly preferred toincorporate the fluorescent brightening agent into the dye-fixingelement or to supply it from the external, for example, from thephotographic material. Examples of the fluorescent brightening agentinclude the compounds described in K. Veenkataraman (compiler), TheChemistry of Synthetic Dyes, Vol. V, Chap. 8, and JP-A-61-143752.Specific examples thereof include stilbene-base compounds, coumarin-basecompounds, biphenyl-base compounds, benzoxazolyl-base compounds,naphthalimido-base compounds, pyrazoline-base compounds andcarbostyryl-base compounds. The fluorescent brightening agent can beused in combination with the discoloration inhibitor.

The hardening agent for use in the constituent layers of thephotographic material or the dye-fixing element includes hardeningagents described in U.S. Pat. No. 4,678,739 (column 41), JP-A-59-116655,JP-A-62-245261 and JP-A-61-18942. Specific examples thereof includealdehyde-base hardening agents (e.g., formaldehyde), aziridine-basehardening agents, epoxy-base hardening agents, vinylsulfone-basehardening agents (e.g., N,N'-ethylenebis(vinylsulfonylacetamido)ethane),N-methylol-base hardening agents (e.g., dimethylolurea) and high polymerhardening agents (e.g., compounds described in JP-A-62-234157).

The constituent layers of the photographic material or the dye-fixingelement may use various surface active agents as a coating aid or forthe purpose of improving releasability or slipperiness, of preventingelectrification or of accelerating development. Specific examples of thesurface active agent are described in JP-A-62-173463 and JP-A-62-183457.

The constituent layers of the photographic material or the dye-fixingelement may use various organic fluoro compounds for improvingslipperiness, preventing electrification or improving releasability.Representative examples of the organic fluoro compound includefluorine-base surface active agents described in JP-B-57-9053 (columns 8to 17), JP-A-61-20944 and JP-A-62-135826, and hydrophobic fluorinecompounds such as oily fluorine-base compounds (e.g., fluorine-containedoil) and solid fluorine compound resins (e.g., ethylene tetrafluorideresin).

The photographic material and the dye-fixing element may use a mattingagent. Examples of the matting agent include the compounds described inJP-A-61-88256 (page (29) ) such as silicon dioxide, polyolefin andpolymethacrylate, and the compounds described in JP-A-63-274944 andJP-A-63-274952 such as benzoguanamine resin beads, polycarbonate resinbeads and AS resin beads. The matting agent may be used not only forpreventing adhesion, controlling slipperiness or inhibiting Newton'sring but also for non-glossing the surface (image surface) of thedye-fixing element.

The constituent layers of the photographic material or the dye-fixingelement may contain a heat solvent, a defoaming agent, anantiseptic/bactericide or colloidal silica. Specific examples of theseadditives are described in JP-A-61-88256 (pages (26) to (32)).

The photographic material or the dye-fixing element may use an imageformation accelerator. The image formation accelerator has a function ofaccelerating the redox reaction of a silver salt oxidizing agent with areducing agent, a function of accelerating the reaction such asproduction or decomposition of a dye from a dye-donating substance orrelease of a diffusible dye, and a function of accelerating the movementof a dye from the photographic material layer to the dye-fixing layer.In view of physicochemical functions, the accelerator is classified intobases or base block compounds, nucleophilic compounds, high boilingpoint organic solvents (oil), heat solvents, surface active agents andcompounds having interaction with silver or silver ion. However, eachgroup of these substances usually has composite functions and alwaysshows several acceleration effects at the same time. These substancesare described in detail in U.S. Pat. No. 4,678,739 (columns 38 to 40).

The base block compound includes salts of an organic acid which isdecarboxylated upon heating, with a base, and compounds which releasesamines by intramolecular nucleophilic substitution reaction, Lossenrearrangement or Beckmann rearrangement. Specific examples thereof aredescribed in U.S. Pat. No. 4,511,493 and JP-A-62-65038.

In a system where heat development and transfer of a dye are performedsimultaneously in the presence of a slight amount of water, the baseand/or the base block compound is preferably incorporated into thedye-fixing element because the storability of the photographic materialcan be increased.

Further, combination of a difficultly soluble metal compound with acompound (called complex-forming compound) capable of complex-formingreaction with the metal ions constituting the difficultly soluble metalcompound described EP-A-210660 and U.S. Pat. No. 4,740,445, andcompounds which generates a base upon electrolysis described inJP-A-61-232451 may also be used as the base block compound.Particularly, the former method is effective. It is advantageous to addthe difficultly soluble metal compound and the complex-forming compoundseparately to the photographic material and to the dye-fixing element.

In the present invention, the photographic material and/or dye-fixingelement may use various development stopping agents for the purpose ofalways obtaining a constant image against fluctuations in the processingtemperature and in the processing time during development.

The term "development stopping agent" as used herein means a compoundwhich smoothly neutralizes or reacts with the base after properdevelopment to reduce the concentration of the base in the layer tothereby stop the development or a compound which interacts with silverand silver salt to inhibit the development. More specifically, thedevelopment stopping agent includes acid block compounds which releasean acid upon heating, electrophilic compounds which cause substitutionreaction with the base present together upon heating,nitrogen-containing heterocyclic compounds, mercapto compounds andprecursors thereof. The development stopping agent is described in moredetail in JP-A-62-253159 (pages (31) and (32)).

In the present invention, as the support of the photographic material orthe dye-fixing element, substances endurable to the processingtemperature are used. In general, paper and synthetic high polymers(film) are used. Specific examples thereof include polyethyleneterephthalate, polycarbonate, polyvinyl chloride, polystyrene,polypropylene, polyimido, celluloses (e.g., triacetyl cellulose) orthose obtained by incorporating a pigment such as titanium oxide intothese films, film synthetic paper made from polypropylene, mixed paperprepared from a synthetic resin pulp such as polyethylene with a naturalpulp, Yankee paper, baryta paper, coated paper (particularly, castcoated paper), metal, cloths and glasses.

These materials each may be used alone or may be used as a supporthaving laminated on one surface or both surfaces thereof with asynthetic high polymer such as polyethylene.

In addition, the supports described in JP-A-62-253159 (pages (29) to(31)) may be used.

On the surface of the above-described support, a hydrophilic binder anda semiconductor metal oxide such as alumina sol or tin oxide, or anantistatic agent such as carbon black may be coated.

The method of exposing and recording an image on the photographicmaterial includes a method of exposing image information with lightemitting diode or various lasers emitted through electrical signals, anda method of outputting image information on an image display such as aCRT, a liquid crystal display, an electroluminescense display or aplasma display and exposing it directly or through an optical system.More specifically, the exposure methods described in JP-A-2-129625,JP-A-5-176144, JP-A-5-199372 and JP-A-6-127021 may be used.

As the light source for use in recording an image on a photographicmaterial, light emitting diode, lasers, CRT and other light sourcesdescribed in U.S. Pat. No. 4,500,626 (column 56) may be used.

The magnetic recording layer which is preferably used in the presentinvention is descried below.

The magnetic recording layer is provided by coating an aqueous ororganic solvent-base coating solution containing a binder havingdispersed therein magnetic particles, on a support.

The magnetic particle includes ferromagnetic iron oxide (e.g., γFe₂ O₃),Co-doped γFe₂ O₃, Co-doped magnetite, Co-containing magnetite,ferromagnetic chromium dioxide, ferromagnetic metal, ferromagneticalloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite and Ca ferrite.Among these, Co-doped ferromagnetic iron oxide such as Co-doped γFe₂ O₃is preferred. The form of the magnetic particle may be any of acicular,rice grain-like, spherical, cubic and platy forms. The specific surfacearea as S_(BET) is preferably 20 m² /g or more, more preferably 30 m² /gor more. The saturation magnetization (σs) of the ferromagnetic materialis preferably from 3.0×10⁴ to 3.0×10⁻⁵ A/m, more preferably from 4.0×10⁴to 2.5×10⁵ A/m. The ferromagnetic particle may be subjected to surfacetreatment with silica and/or alumina or an organic material. Further,the ferromagnetic particle may be subjected to surface treatment with asilane coupling agent or a titanium coupling agent as described inJP-A-6-161032. Also, a magnetic particle having coated on the surfacethereof an inorganic or organic material described in JP-A-4-259911 andJP-A-5-81652 may be used.

The binder for use in the magnetic particle includes a thermoplasticresin, a thermosetting resin, a radiation-curable resin, a reactiveresin, an acid, alkali or biodegradable polymer, a natural polymer(e.g., cellulose derivative, saccharide derivative) and a mixture ofthese described in JP-A-4-219569. The above-described resin has a Tg offrom -40° C. to 300° C. and a weight average molecular weight of from2,000 to 1,000,000. Examples of the resin include a vinyl copolymer, acellulose derivative such as cellulose diacetate, cellulose triacetate,cellulose acetate propionate, cellulose acetate butyrate and cellulosetripropionate, an acrylic resin and a polyvinyl acetal resin, andgelatin is also preferably used. Among these, cellulose di(tri)acetateis preferred. The binder may cured by adding thereto an epoxy-base,aziridine-base or isocyanate-base crosslinking agent. Examples of theisocyanate-base crosslinking agent include isocyanates such astolylenediisocyanate, 4,4'-diphenylmethanediisocyanate,hexamethylenediisocyanate and xylylenediisocyanate, a reaction productof these isocyanates with polyalcohol (e.g., a reaction product of 3 molof tolylenediisocyanate with 1 mol of trimethylolpropane) and apolyisocyanate produced by the condensation of these isocyanates, whichare described, for example, in JP-A-6-59357.

The ferromagnetic material is dispersed into the binder by the methodpreferably using a kneader, a pin-type mill or an annular-type mill asdescribed in JP-A-6-35092 and these may also be preferably used incombination. The dispersant described in JP-A-5-088283 and other knowndipersants may be used. The thickness of the magnetic recording layer isfrom 0.1 to 10 μm, preferably from 0.2 to 5 μm, more preferably from 0.3to 3 μm. The weight ratio of the magnetic particle to the binder ispreferably from 0.5:100 to 60:100, more preferably from 1:100 to 30:100.The coating amount of magnetic particles is from 0.005 to 3 g/m²,preferably from 0.01 to 2 g/m², more preferably from 0.02 to 0.5 g/m².The magnetic recording layer has a transmitted yellow density ofpreferably from 0.01 to 0.50, more preferably from 0.03 to 0.20, stillmore preferably from 0.04 to 0.15. The magnetic recording layer may beprovided throughout the entire surface of or stripedly on the backsurface of the photographic support by coating or printing. The magneticrecording layer can be coated by using air doctor, blade, air knife,squeeze, soakage, reverse roller, transfer roller, gravure, kiss, cast,spray, dip, bar or extrusion, and the coating solution described inJP-A-5-341436 is preferred.

The magnetic recording layer may be designed to have additionalfunctions such as improvement of lubricity, control of curl,electrostatic charge prevention, prevention of adhesion or headabrasion, or other functional layers may be provided to undertake thesefunctions. At least one or more of particles is preferably an abrasiveas an aspheric inorganic particle having a Mhos' hardness of 5 or more.The composition of the aspheric inorganic particle is preferably anoxide such as aluminum oxide, chromium oxide, silicon dioxide ortitanium dioxide, a carbide such as silicon carbide or titanium carbide,or a fine particle of diamond. The abrasive may be subjected to surfacetreatment with a silane coupling agent or a titanium coupling agent. Theparticles may be added to a magnetic recording layer or may beovercoated on the magnetic recording layer (for example, as a protectivelayer or a lubricant layer). The binder used here may be those describedabove and it is preferably the same as the binder in the magneticrecording layer. The photographic material having a magnetic recordinglayer is described in U.S. Pat. Nos. 5,336,589, 5,250,404, 5,229,259 and5,215,874 and European Patent 466130.

The polyester support which is preferably used in the present inventionis described below. The details thereon including the photographicmaterial, the processing, the cartridge and the experimental examplesare described in JIII Journal of Technical Disclosure No. 94-6023 (Mar.15, 1994). The polyester is essentially constituted by a diol and anaromatic dicarboxylic acid. Examples of the aromatic dicarboxylic acidinclude 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylicacid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylicacid, terephthalic acid, isophthalic acid and phthalic acid, andexamples of the diol include diethylene glycol, triethylene glycol,cyclohexanedimethanol, bisphenol A and biphenol. The polymer polymerizedfrom these includes homopolymers such as polyethylene terephthalate,polyethylene naphthalate and polycyclohexanedimethanol terephthalate.Among these, preferred is a polyester containing from 50 to 100 mol % of2,6-naphthalenedicarboxylic acid. Particularly preferred is polyethylene2,6-naphthalate. The average molecular weight is approximately from5,000 to 200,000. The polyester for use in the present invention has aTg of 50° C. or higher, more preferably 90° C. or higher.

The polyester support is then subjected to heat treatment to refuse tohave curling habit at a heat treatment temperature of from 40° C. toless than Tg, more preferably from (Tg-20° C.) to less than Tg. The heattreatment may be conducted either at a constant temperature within theabove-described range or while cooling. The heat treatment time is from0.1 to 1,500 hours, more preferably from 0.5 to 200 hours. The supportmay be subjected to heat treatment either in a state of roll or as a webalong the conveyance. The surface may be made uneven (for example, bycoating electrically conductive inorganic fine particles such as SnO₂ orSb₂ O₅)) to improve the surface state. Also, it is preferred to makesome designs such that the edge is knurled to slightly increase theheight only of the edge, thereby preventing the difference in level dueto the edge from imparting the evenness of support wound thereon. Theheat treatment may be conducted at any stage of after formation ofsupport film, after surface treatment, after coating of a back layer(e.g., antistatic agent, slipping agent) and after coating of anundercoat layer. The preferred stage is after coating of an antistaticagent.

Into the polyester, an ultraviolet absorbent may be kneaded in. Or, forpreventing light piping, a commercially available dye or pigment forpolyester, such as Diaresin produced by Mitsubishi Kasei Corporation orKayaset produced by Nippon Kayaku K.K., may be mixed so as to attain thepurpose.

The surface treatment is preferably conducted so that the support can bebonded to the photographic material constituent layer. Examples of thesurface activation treatment include chemical treatment, mechanicaltreatment, corona discharge treatment, flame treatment, ultravioletlight treatment, high frequency treatment, glow discharge treatment,active plasma treatment, laser treatment, mixed acid treatment and ozoneoxidation treatment. Among these surface treatments, preferred areultraviolet irradiation treatment, flame treatment, corona treatment andglow treatment.

The undercoating method is described below. The undercoating may besingle layer coating or two or more layer coating. The binder for theundercoat layer includes a copolymer starting from a monomer selectedfrom vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,acrylic acid, itaconic acid and maleic anhydride, and in addition,polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose andgelatin. The compound which expands the support include resorcin andp-chlorophenol. The undercoat layer may contain a gelatin hardeningagent and examples thereof include chromic salts (e.g., chrome alum),aldehydes (e.g., formaldehyde, glutaraldehyde), isocyanates, activehalogen compounds (e.g., 2,4-dichloro-6-hydroxy-S-triazine),epichlorohydrin resin and active vinyl sulfone compounds. Further, theundercoat layer may contain an inorganic fine particle such as SiO₂ orTiO₂, or a polymethyl methacrylate copolymer fine particle (0.01 to 10μm), as a matting agent.

The antistatic agent which is preferably used in the present inventionincludes high polymers containing a carboxylic acid, a carboxylate or asulfonate, cationic high polymers and ionic surface active agentcompounds.

Most preferred antistatic agents are fine particles of at least onecrystalline metal oxide having a volume resistivity of 10⁷ Ω·cm or less,more preferably 10⁵ Ω·cm or less and a particle size of from 0.001 to1.0 μm, selected from ZnO, TiO₂, SnO₂, Al₂ O₃, In₂ O₃, SiO₂, MgO, BaO,MoO₃ and V₂ O₅, or of a composite oxide of these (e.g., Sb, P, B, In, S,Si, C), and fine particles of a sol-like metal oxide or of a compositeoxide of these. The content of the antistatic agent in the photographicmaterial is preferably from 5 to 500 mg/m², more preferably from 10 to350 mg/m². The ratio of the electrically conductive crystalline oxide ora composite oxide thereof to the binder is preferably from 1/300 to100/1, more preferably from 1/100 to 100/5.

The photographic material of the present invention preferably hasslipperiness. The slipping agent-containing layer is preferably providedon both of the light-sensitive layer surface and the back surface. Thepreferred slipperiness is in terms of a coefficient of dynamic friction,from 0.01 to 0.25. The value is determined using a stainless steel ballhaving a diameter of 5 mm while transporting the photographic materialat a speed of 60 cm/min (25° C., 60% RH). In this evaluation, even whenthe other party is changed to the light-sensitive layer surface, thevalue almost on the same level is obtained.

The slipping agent which can be used in the present invention includespolyorganosiloxane, a higher fatty acid amide, a higher fatty acid metalsalt and an ester of a higher fatty acid with a higher alcohol. Examplesof the polyorganosiloxane include polydimethylsiloxane,polydiethylsiloxane, polystyrylmethylsiloxane andpolymethylphenylsiloxane. The layer to which the slipping agent is addedis preferably an outermost layer of the emulsion layer or a back layer.In particular, polydimethylsiloxane and an ester having a long chainalkyl group are preferred.

The photographic material of the present invention preferably contains amatting agent. The matting agent may be provided either on the emulsionsurface or on the back surface, but it is particularly preferably addedto the outermost layer on the emulsion layer side. The matting agent maybe either soluble or insoluble in the processing solution, andpreferably, both of these two kinds of matting agents are used incombination. For example, polymethyl methacrylate, poly(methylmethacrylate/methacrylic acid=9/1 or 5/5 (by mol)) and polystyreneparticles are preferred. The particle size is preferably from 0.8 to 10μm, the particle size distribution is preferably narrower, and 90% bynumber or more of all particles preferably have a size between 0.9 and1.1 times the average particle size. In order to increase the mattingproperty, fine particles of 0.8 μm or less are preferably added at thesame time and examples thereof include polymethyl methacrylate (0.2 μm),poly(methyl methacrylate/methacrylic acid=9/1 (by mol), 0.3 μm),polystyrene particles (0.25 μm) and colloidal silica (0.03 μm).

The film patrone which is preferably used for the present invention isdescribed below. The patrone may use a metal or a synthetic plastic as amain material.

Preferred plastic materials are polystyrene, polyethylene, polypropyleneand polyphenyl ether. The patrone of the present invention may furthercontain various antistatic agents and preferred examples thereof includecarbon black, metal oxide particles, nonionic, anionic, cationic andbetaine surface active agents and polymers. The patrone imparted withthe antistatic property is described in JP-A-1-312537 and JP-A-1-312538.In particular, the resistance at 25° C. and 25% RH is preferably 10¹² Ωor less. Usually, the plastic patrone is produced using a plastic havingkneaded therein carbon black or a pigment so as to give light-shieldingproperty. The patrone may be in a 135 size currently used but, inachieving down-sizing of camera, it is also effective to reduce thecartridge size from 25 mm of 135 size currently populated to 22 mm orless. The volume of the patrone case is preferably 30 cm³ or less, morepreferably 25 cm³ or less. The weight of plastics used in the patroneand the patrone case is preferably from 5 to 15 g.

A patrone which sends forth the film by the rotation of a spool may beused. Also, the patrone may have such a constitution that a film leadingend is housed in the patrone body and the film leading end is sent forthfrom the port part of the patrone to the outside by rotating the spoolshaft in the film delivery direction. These are disclosed in U.S. Pat.Nos. 4,834,306 and 5,226,613. The photographic film for use in thepresent invention may be a so-called green film before development or adeveloped photographic film. Also, a green film and a developedphotographic film may be housed in the same new patrone or in differentpatrones.

The present invention is described below in greater detail withreference to the Examples, however, the present invention should not beconstrued as being limited thereto.

EXAMPLE 1

Sample 101 as a multi-layer color photographic material was prepared tohave layers each having the following composition, on a cellulosetriacetate film support subjected to undercoating.

Composition of Light-Sensitive Layer

The coating amounts are expressed, in the case of silver halide andcolloid silver, by the unit of g/m² of silver, in the case of couplers,additives and gelatin, by the unit of g/m² and, in the case ofsensitizing dyes, by molar number per mol of silver halide in the samelayer. The symbols used for additives have the following meanings. Whenthe additive has a plurality of effects, one of the effects is used as arepresentative.

    ______________________________________                                               UV:  ultraviolet absorbent,                                                   Solv:                                                                              high boiling point organic solvent                                       ExF: dye                                                                      ExS: sensitizing dye                                                          ExC: cyan coupler                                                             ExM: magenta coupler                                                          ExY: yellow coupler                                                           Cpd: additive                                                          First Layer (antihalation layer)                                              Black colloidal silver          0.18                                          Gelatin                         2.10                                          UV-1                            1.9 × 10.sup.-2                         UV-2                            4.0 × 10.sup.-2                         UV-3                            8.6 × 10.sup.-2                         ExF-3                           5.0 × 10.sup.-3                         ExM-3                           2.3 × 10.sup.-2                         Solv-1                          0.16                                          Solv-2                          0.10                                          Second Layer (interlayer)                                                     Gelatin                         0.88                                          Polyethylacrylate latex         2.6 × 10.sup.-1                         ExC-7                           5.0 × 10.sup.-2                         Third Layer (low-sensitivity red-sensitive emulsion                           layer)                                                                        Silver Iodobromide Emulsion A                                                                         as silver                                                                             0.20                                          Silver Iodobromide Emulsion B                                                                         as silver                                                                             0.60                                          Gelatin                         1.75                                          ExS-1                           6.9 × 10.sup.-4                         ExS-2                           4.0 × 10.sup.-4                         ExS-5                           6.7 × 10.sup.-4                         ExS-7                           1.4 × 10.sup.-5                         ExC-1                           3.2 × 10.sup.-1                         ExC-5                           2.2 × 10.sup.-1                         ExC-9                           2.2 × 10.sup.-2                         Cpd-4                           5.3 × 10.sup.-2                         ExC-4                           6.1 × 10.sup.-2                         Fourth Layer (medium-sensitivity red-sensitive                                emulsion layer)                                                               Silver Iodobromide Emulsion C                                                                         as silver                                                                             0.72                                          Gelatin                         0.98                                          ExS-1                           3.5 × 10.sup.-4                         ExS-2                           2.0 × 10.sup.-4                         ExS-5                           3.4 × 10.sup.-4                         ExS-7                           6.9 × 10.sup.-6                         ExC-1                           1.0 × 10.sup.-1                         ExC-3                           1.0 × 10.sup.-2                         ExC-4                           4.3 × 10.sup.-2                         ExC-5                           8.6 × 10.sup.-2                         ExC-6                           1.1 × 10.sup.-2                         ExC-7                           4.6 × 10.sup.-2                         Cpd-4                           2.1 × 10.sup.-2                         Fifth Layer (high-sensitivity red-sensitive emulsion                          layer)                                                                        Silver Iodobromide Emulsion D                                                                         as silver                                                                             0.63                                          Gelatin                         0.65                                          ExS-1                           3.2 × 10.sup.-4                         ExS-2                           1.8 × 10.sup.-4                         ExS-5                           3.1 × 10.sup.-4                         ExS-7                           4.8 × 10.sup.-5                         ExC-1                           4.8 × 10.sup.-1                         ExC-6                           9.0 × 10.sup.-3                         ExC-4                           1.8 × 10.sup.-2                         ExC-8                           5.0 × 10.sup.-3                         ExC-9                           1.0 × 10.sup.-2                         Cpd-4                           2.1 × 10.sup.-3                         Solv-1                          0.08                                          Solv-2                          0.04                                          Sixth Layer (interlayer)                                                      Gelatin                         0.62                                          Cpd-1                           0.08                                          Polyethylacrylate latex         4.1 × 10.sup.-2                         Solv-1                          4.0 × 10.sup.-2                         Seventh Layer (low-sensitivity green-sensitive                                emulsion layer)                                                               Silver Iodobromide Emulsion E                                                                         as silver                                                                             0.14                                          Gelatin                         0.49                                          ExS-8                           5.7 × 10.sup.-5                         ExS-4                           9.0 × 10.sup.-4                         ExS-5                           1.8 × 10.sup.-4                         ExM-1                           0.26                                          Solv-1                          0.15                                          Solv-3                          7.0 × 10.sup.-3                         Eighth Layer (medium-sensitivity green-sensitive                              emulsion layer)                                                               Silver Iodobromide Emulsion F                                                                         as silver                                                                             0.10                                          Silver Iodobromide Emulsion E                                                                         as silver                                                                             0.01                                          Gelatin                         0.14                                          ExS-8                           4.3 × 10.sup.-5                         ExS-4                           6.8 × 10.sup.-4                         ExS-5                           1.3 × 10.sup.-4                         ExM-1                           4.7 × 10.sup.-2                         ExM-4                           2.0 × 10.sup.-3                         ExM-7                           1.0 × 10.sup.-2                         ExY-1                           5.0 × 10.sup.-3                         Solv-1                          3.3 × 10.sup.-2                         Solv-3                          1.5 × 10.sup.-3                         Ninth Layer (high-sensitivity green-sensitive                                 emulsion layer)                                                               Silver Iodobromide Emulsion G                                                                         as silver                                                                             0.58                                          Gelatin                         0.60                                          ExS-4                           5.0 × 10.sup.-4                         ExS-5                           9.9 × 10.sup.-5                         ExS-8                           3.2 × 10.sup.-5                         ExM-7                           2.2 × 10.sup.-2                         ExM-1                           8.0 × 10.sup.-2                         ExM-5                           1.0 × 10.sup.-2                         ExM-6                           5.0 × 10.sup.-3                         ExY-1                           6.7 × 10.sup.-2                         ExC-1                           6.0 × 10.sup.-3                         ExC-4                           8.0 × 10.sup.-3                         Cpd-6                           8.0 × 10.sup.-3                         Solv-1                          0.12                                          Solv-2                          0.06                                          Solv-3                          6.0 × 10.sup.-3                         Tenth Layer (interlayer)                                                      Gelatin                         0.39                                          UV-2                            1.4 × 10.sup.-2                         UV-3                            1.6 × 10.sup.-2                         UV-5                            4.2 × 10.sup.-2                         Cpd-1                           2.6 × 10.sup.-2                         Polyethylacrylate latex         1.4 × 10.sup.-2                         Solv-1                          2.8 × 10.sup.-2                         Eleventh Layer (donor layer having interlayer effect                          to red-sensitive layer)                                                       Silver Iodobromide Emulsion H                                                                         as silver                                                                             1.10                                          Silver Iodobromide Emulsion I                                                                         as silver                                                                             0.24                                          Gelatin                         1.61                                          ExS-3                           6.4 × 10.sup.-4                         ExM-2                           2.7 × 10.sup.-2                         ExM-1                           1.8 × 10.sup.-1                         ExM-7                           1.5 × 10.sup.-1                         ExY-2                           2.0 × 10.sup.-1                         Solv-1                          0.50                                          Twelfth Layer (yellow filter layer)                                           Yellow colloidal silver         3.3 × 10.sup.-2                         Gelatin                         0.61                                          Cpd-1                           4.3 × 10.sup.-2                         Cpd-2                           7.9 × 10.sup.-2                         Cpd-5                           1.0 × 10.sup.-3                         Solv-1                          4.7 × 10.sup.-2                         Thirteenth Layer (low-sensitivity blue-sensitive                              emulsion layer)                                                               Silver Iodobromide Emulsion J                                                                         as silver                                                                             0.60                                          Gelatin                         1.65                                          ExS-9                           8.8 × 10.sup.-4                         ExY-2                           1.2 × 10.sup.-1                         ExY-3                           5.0 × 10.sup.-1                         ExC-9                           4.0 × 10.sup.-2                         ExY-5                           5.0 × 10.sup.-2                         ExY-7                           2.0 × 10.sup.-2                         ExY-8                           1.0 × 10.sup.-2                         ExC-1                           3.0 × 10.sup.-2                         ExC-10                          8.4 × 10.sup.-2                         Solv-1                          0.33                                          Fourteenth Layer (high-sensitivity blue-sensitive                             emulsion layer)                                                               Silver Iodobromide Emulsion K                                                                         as silver                                                                             0.20                                          Silver Iodobromide Emulsion L                                                                         as silver                                                                             0.15                                          Silver Iodobromide Emulsion M                                                                         as silver                                                                             0.22                                          Gelatin                         1.00                                          ExS-6                           4.4 × 10.sup.-4                         ExY-2                           7.6 × 10.sup.-2                         ExY-3                           1.3 × 10.sup.-1                         ExY-6                           3.2 × 10.sup.-1                         ExY-8                           4.0 × 10.sup.-2                         ExC-1                           1.8 × 10.sup.-2                         ExC-10                          2.3 × 10.sup.-2                         Solv-1                          1.7 × 10.sup.-1                         Fifteenth Layer (first protective layer)                                      Fine Grain Silver       as silver                                                                             0.06                                          Iodobromide Emulsion N                                                        Gelatin                         0.51                                          UV-2                            4.0 × 10.sup.-2                         UV-3                            4.9 × 10.sup.-2                         UV-4                            0.02                                          UV-5                            0.12                                          Cpd-3                           0.10                                          ExF-4                           2.1 × 10.sup.-3                         ExF-5                           6.3 × 10.sup.-3                         Solv-4                          2.0 × 10.sup.-2                         Polyethylacrylate latex         9.0 × 10.sup.-2                         Sixteenth Layer (second protective layer)                                     Fine Grain Silver       as silver                                                                             0.18                                          Iodobromide Emulsion N                                                        Gelatin                         0.84                                          B'-1 (diameter: 2.0 μm)      8.0 × 10.sup.-2                         B'-2 (diameter: 2.0 μm)      8.0 × 10.sup.-2                         B'-3                            3.0 × 10.sup.-2                         W-5                             1.8 × 10.sup.-2                         H-1                             0.18                                          ______________________________________                                    

To the thus-prepared sample, 1,2-benzoisothiazolin-3-one (200 ppm onaverage to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm onaverage to gelatin) and 2-phenoxyethanol (about 10,000 ppm on average togelatin) were additionally added. Further, in order to provide goodpreservability, processability, pressure durability,antimold/bactericidal property, antistatic property and coatability,W-1, W-2, W-3, W-4, W-5, W-6, B'-1, B'-2, B'-3, B'-4, B'-5, B'-6, F-1,F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14,F-15, F-16, F-17, iron salt, lead salt, gold salt, platinum salt,iridium salt or rhodium salt was appropriately added to each layer.

                                      TABLE 1                                     __________________________________________________________________________    Average   Average Grain                                                       AgI       Size Sphere-                                                                          Coefficient of                                                                       Diameter/                                                                          Silver Amount Ratio                             Content   Corresponding                                                                         Variation in                                                                         Thickness                                                                           core/medium/shell!                                                                    Grain                                  (mol %)   Diameter (μm)                                                                      Grain Size (%)                                                                       Ratio                                                                              (AgI content)                                                                          Structure/Form                         __________________________________________________________________________    Emulsion A                                                                          4.7 0.40    10     1.0   40/10/50!                                                                         (1/38/1)                                                                          triple structure,                                                             cubic grain                            Emulsion B                                                                          1.7 0.46    15     5.5   5/55/40!                                                                          (5/2/2)                                                                           triple structure,                                                             tabular grin                           Emulsion C                                                                          7.9 0.53    18     4.0   6/45/49!                                                                          (2/8/9)                                                                           triple structure,                                                             tabular grin                           Emulsion D                                                                          8.8 0.65    15     3.5   12/59/29!                                                                         (0/12/6)                                                                          triple structure,                                                             tabular grin                           Emulsion E                                                                          1.7 0.46    15     5.0   5/55/40!                                                                          (5/2/2)                                                                           triple structure,                                                             tabular grin                           Emulsion F                                                                          7.9 0.51    18     4.0   6/45/49!                                                                          (2/8/9)                                                                           triple structure,                                                             tabular grin                           Emulsion G                                                                          3.5 0.55    15     3.5   12/59/29!                                                                         (0/5/2)                                                                           triple structure,                                                             tabular grin                           Emulsion H                                                                          8.0 0.65    28     2.5   33/67!                                                                            (18/3)                                                                            double structure,                                                             platy grain                            Emulsion I                                                                          10.3                                                                              0.40    15     1.0   25/75!                                                                            (29/4)                                                                            double structure,                                                             octahedral grain                       Emulsion J                                                                          1.7 0.52    15     4.2   5/55/40!                                                                          (5/2/2)                                                                           triple structure,                                                             tabular grain                          Emulsion K                                                                          8.8 0.64    23     5.2   7/64/29!                                                                          (0/11/8)                                                                          triple structure,                                                             tabular grain                          Emulsion L                                                                          3.4 0.80    18     4.7   12/56/32!                                                                         (0/1/9)                                                                           triple structure,                                                             tabular grain                          Emulsion M                                                                          13.9                                                                              1.30    25     3.0   35/65!                                                                            (34/3)                                                                            double structure,                                                             platy grain                            Emulsion N                                                                          2.0 0.07    15     1.0  --       uniform structure,                                                            fine grain                             __________________________________________________________________________

In Table 1:

(1) Emulsions A to M were subjected to reduction sensitization at thegrain preparation using thiourea dioxide and thiosulfonic acid accordingto the example of JP-A-2-191938 (corresponding to U.S. Pat. No.5,061,614);

(2) Emulsions A to M were subjected to gold sensitization, sulfursensitization and selenium sensitization in the presence of the spectralsensitizing dyes described in each light-sensitive layer and sodiumthiocyanate according to the example of JP-A-3-237450 (corresponding toEP-A-443453);

(3) in the preparation of tabular grains, low molecular weight gelatinwas used according to the example of JP-A-1-158426;

(4) in tabular grains and regular crystal grains having a grainstructure, dislocation lines were observed through a high-pressureelectron microscope as described in JP-A-3-237450; and

(5) Emulsions A to M contain iridium incorporated inside the grainaccording to the method described in B. H. Carroll, Photographic Scienceand Engineering, 24, 265 (1980). ##STR92##

To the fourth layer of Sample 101, the compound represented by formula(IA) or a comparative compound, coemulsified with the coupler in thislayer, was added to give the coated amount of 1.5×10⁻² mol per mol of Agin this layer. Samples 102 to 111 as shown in Table 2 were prepared byfollowing the preparation method of Sample 101 with respect to otherconditions. When two compounds are indicated, they are used as a 1:1 bymol mixture and added to give the coated amount, in terms of the totalmolar number, of 1.5×10⁻² mol/mol-Ag.

Evaluation on the fluctuation in the photographic property afterphotographing until processing was performed in the following manner.

Each photographic material sample was exposed for sensitometry, storedfor 3 days under forcedly deteriorating conditions of 50° C. and 60% orof 40° C. and 80%, and then subjected to the following color developmentprocessing at 38° C. The processed samples were measured on the densitythrough a red filter and a blue filter. The degree of difference in thesensitivity between these samples and the sample subjected todevelopment processing immediately after exposure was evaluated.

Each of the color photographic materials was exposed as above and thenprocessed according to the following method.

    ______________________________________                                        Processing Method                                                             Step        Processing Time                                                                           Processing Temperature (°C.)                   ______________________________________                                        Color development                                                                         3 min.  15 sec. 38                                                Bleaching   3 min.  00 sec. 38                                                Water washing       30 sec. 24                                                Fixing      3 min.  00 sec. 38                                                Water washing (1)   30 sec. 24                                                Water washing (2)   30 sec. 24                                                Stabilization       30 sec. 38                                                Drying      4 min.  20 sec. 55                                                ______________________________________                                    

The composition of each processing solution is shown below.

    ______________________________________                                                                 (unit: g)                                            ______________________________________                                        (Color Developer)                                                             Diethylenetriaminepentaacetic acid                                                                       1.0                                                1-Hydroxyethylidene-1,1-diphosphonic acid                                                                3.0                                                Sodium sulfite             4.0                                                Potassium carbonate        30.0                                               Potassium bromide          1.4                                                Potassium iodide           1.5    mg                                          Hydroxylamine sulfate      2.4                                                4- N-Ethyl-N-β-hydroxyethylamino!-2-methylaniline                                                   4.5                                                sulfate                                                                       Water to make              1.0    liter                                       pH                         10.05                                              (Bleaching Solution)                                                          Sodium ethylenediaminetetraacetato ferrate trihydrate                                                    100.0                                              Disodium ethylenediaminetetraacetate                                                                     10.0                                               3-Mercapto-1,2,4-triazole  0.03                                               Ammonium bromide           140.0                                              Ammonium nitrate           30.0                                               Aqueous ammonia (27%)      6.5    ml                                          Water to make              1.0    liter                                       pH                         6.0                                                (Fixing Solution)                                                             Disodium ethylenediaminetetraacetate                                                                     0.5                                                Ammonium sulfite           20.0                                               Ammonium thiosulfate (aq. soln. 700 g/l)                                                                 295.0                                              Acetic acid (90%)          3.3                                                Water to make              1.0    liter                                       pH                         6.7                                                (Stabilizing Solution)                                                        p-Nonylphenoxypolyglycidol (glycidol average                                                             0.2                                                polymerization degree: 10)                                                    Ethylenediaminetetraacetic acid                                                                          0.05                                               1,2,4-Triazole             1.3                                                1,4-Bis(1,2,4-triazol-1-ylmethyl)piperazine                                                              0.75                                               Hydroxyacetic acid         0.02                                               Hydroxyethyl cellulose (HEC SP-2000, produced by Daicel                                                  0.1                                                Chemical KK)                                                                  1,2-Benzoisothiazolin-3-one                                                                              0.05                                               Water to make              1.0    liter                                       pH                         8.5                                                ______________________________________                                    

The sensitivity as a photographic property is shown by a logarithm ofthe reciprocal of an exposure amount required to give an optical density1.0 higher than the fog. The fluctuation in the photographic propertyafter photographing until processing is shown by a relative sensitivity(difference in logarithms) of the sensitivity of photographic materialsstored after exposure under forcedly deteriorating conditions to thesensitivity of the photographic material processed immediately afterexposure. The nearer to 0 the value is, the smaller the fluctuation inthe photographic property is and the more preferable the material is.

Fluctuation in the photographic property both of the red-sensitive layerto which the compound of formula (IA) was added and of theblue-sensitive layer to which the compound was not added was evaluated.When the compound of formula (IA) or a comparative compound was added,the photographic property of the blue-sensitive layer changed ascompared with the material (Sample 101) to which the compound was notadded. This reveals that the compound disadvantageously diffused fromthe red-sensitive layer (layer to which the compound was added) to theblue-sensitive layer (layer to which the compound was not added).

The results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Compound A (Compound described in JP-A-59-198453                               ##STR93##                                                                                 Fluctuation in Photographic                                                   Property due to Aging after                                                   Photopraphing until Processing                                                Red-Sensitive                                                                            Blue-Sensitive                                                     Layer      layer                                                                    50° C.,                                                                        40° C.,                                                                       50° C.,                                                                      40° C.,                        Sample   Compound  60%     80%    60%   80%                                   ______________________________________                                        101      --        0.15    -0.02  -0.01 -0.02                                 (Comparison)                                                                  102      A         0.10    -0.02  -0.03 -0.09                                 (Comparison)                                                                  103      A-1       0.02    -0.02  -0.01 -0.02                                 (Invention)                                                                   104      A-23      0.06    -0.02  -0.01 -0.02                                 (Invention)                                                                   105      A-33      0.02    -0.02  -0.01 -0.02                                 (Invention)                                                                   106      A-4       0.02    -0.02  -0.01 -0.02                                 (Invention)                                                                   107      A-17      0.02    -0.02  -0.01 -0.02                                 (Invention)                                                                   108      A-27      0.03    -0.02  -0.01 -0.02                                 (Invention)                                                                   109      A-40      0.03    -0.02  -0.01 -0.02                                 (Invention)                                                                   110      A-44      0.02    -0.02  -0.01 -0.02                                 (Invention)                                                                   111      A-46      0.03    -0.02  -0.01 -0.02                                 (Invention)                                                                   ______________________________________                                    

As clearly seen from Table 2, the photographic materials using thecompound of formula (IA) according to the present invention showed goodresults such that fluctuation in the photographic property due to agingafter photographing until processing of the layer to which the compoundwas added (red-sensitive layer) was small and at the same time,fluctuation due to aging of the layer to which the compound was notadded (blue-sensitive layer) was not worsened.

The compound of formula (IA) according to the present invention affectedneither other photographic properties nor storability of the layer towhich the compound was not added.

EXAMPLE 2

Other than the compounds shown in Table 2 of Example 1, using CompoundA-2, A-3, A-5, A-6, A-7, A-8, A-9, A-10, A-11, A-12, A-13, A-14, A-15,A-16, A-18, A-19, A-20, A-21, A-22, A-24, A-25, A-26, A-28, A-29, A-30,A-31, A-32, A-34, A-35, A-36, A-37, A-38, A-39, A-41, A-42, A-43, A-45or A-46 for use in the present invention, evaluation of red-sensitivelayer or green-sensitive layer was conducted. As a result, thesecompounds provided advantageous results such that the change in thephotographic property due to aging was reduced when the materials wereallowed to stand after photographing.

EXAMPLE 3

When the compound for use in the present invention was used in thegreen-sensitive layer or the blue-sensitive layer, similarly to Example.1, good results were provided such that the storability of the layer towhich the compound was added was improved and the layer to which thecompound was not added was not affected.

EXAMPLE 4

Sample 401 was prepared in place of Sample 101 of Example 1.

Samples 402 to 411 corresponding to Samples 102 to 111 were preparedaccording to the preparation method of Sample 401 except that to thefourth layer of Sample 401, the compound represented by formula (IA) ora comparative compound, coemulsified with the coupler in this layer, wasadded to give the coated amount of 5×10⁻² mol per mol of Ag in thislayer (Sample 402 is a comparative example).

When two compounds are indicated, they are used as a 1:1 by mol mixtureand added to give the coated amount, in terms of the total molar number,of 5×10⁻² mol/mol-AgX.

Using these samples, evaluation of the compounds for use in the presentinvention was conducted and as a result, good capability was exhibitedsimilarly to Example 1.

1) Support

The support used in this example was prepared according to the followingmethod.

Polyethylene-2,6-naphthalate polymer (100 parts by weight) and 2 partsby weight of Tinuvin P.326 (produced by Ciba Geigy AG) as an ultravioletabsorbent were dried, melted at 300° C., extracted from a T-die,stretched in the machine direction at 140° C. to 3.3 times, thenstretched in the transverse direction at 130° C. to 3.3 times andfurther heat set at 250° C. for 6 seconds to obtain a PEN film having athickness of 90 μm. To the resulting PEN film, a blue dye, a magenta dyeand a yellow dye (Compounds I-1, I-4, I-6, I-24, I-26, I-27 and II-5described in JIII Journal of Technical Disclosure, No. 94-6023) wereadded in an appropriate amount. Further, the film was wound around astainless steel core having a diameter of 20 cm to have heat history at110° C. for 48 hours, thereby obtaining a support difficult of curlinghabit.

2) Coating of undercoat layer

Both surfaces of the support obtained above was subjected to coronadischarge treatment, UV discharge treatment and glow dischargetreatment, and an undercoating solution containing 0.1 g/m² of gelatin,0.01 g/m² of sodium a-sulfodi-2-ethylhexylsuccinate, 0.04 g/m² ofsalicylic acid, 0.2 g/m² of p-chlorophenol, 0.012 g/m² of (CH₂ =CHSO₂CH₂ CH₂ NHCO)₂ CH₂ and 0.02 g/m² of a polyamido-epichlorohydrinpolycondensate was coated (10 ml/m², using a bar coater) on one surfaceto provide an undercoat layer on the higher temperature side at the timeof stretching. The drying was conducted at 115° C. for 6 minutes(rollers and the conveyance device in the drying zone all were heated to115° C.).

3) Coating of back layer

On one surface of the undercoated support, an antistatic layer, amagnetic recording layer and a slipping layer each having the followingcomposition were coated as a back layer.

3-1) Coating of antistatic layer

A fine particle powder dispersion having a resistivity of 5 Ω·cm of atin oxide-antimony oxide composite having an average particle diameterof 0.005 μm (secondary aggregate particle size: about 0.08 μm) wascoated in an amount of 0.2 g/m² together with 0.05 g/m² of gelatin, 0.02g/m² of (CH₂ =CHSO₂ CH₂ CH₂ NHCO)₂ CH₂, 0.005 g/m² ofpoly(polymerization degree: 10)oxyethylene-p-nonylphenol and 0.22 g/m²of resorcin.

3-2) Coating of magnetic recording layer

Co-γ-iron oxide (0.06 g/m²) (specific surface area: 43 m² /g; longeraxis: 0.14 μm; single axis: 0.03 μm; saturated magnetization: 89 emu/g;Fe⁺² /Fe⁺³ =6/94; the surface being treated with aluminum oxide andsilicon oxide each in an amount of 2 wt % based on iron oxide) subjectedto covering treatment with 3-poly(polymerization degree: 15)oxyethylene-propyloxytrimethoxysilane (15 wt %) and dispersed in 1.2g/m² of diacetyl cellulose (the iron oxide being dispersed by an openkneader and sand mill) and 0.3 g/m² of C₂ H₅ C(CH₂ OCONH--C₆ H₃(CH₃)NCO)₃ as a hardening agent were coated using acetone, methyl ethylketone and cyclohexanone as solvents by means of a bar coater to obtaina magnetic recording layer having a thickness of 1.2 μm. Silicaparticles (0.3 μm) as a matting agent and an alumina oxide (0.15 μm)subjected to covering treatment with 3-poly(polymerization degree:15)oxyethylene-propyloxytrimethoxysilane (15 wt %) as an abrasive eachwas added to give a coverage of 10 mg/m². The drying was conducted at115° C. for 6 minutes (rollers and the conveyance device in the dryingzone all were heated to 115° C.). The increase in color density of themagnetic recording layer D^(B) with X-light (blue filter) was about 0.1,the saturated magnetization moment of the magnetic recording layer was4.2 emu/m², the coercive force was 7.3×10⁴ A/m and the angular ratio was65%.

3-3) Preparation of slipping layer

Diacetyl cellulose (25 mg/m²) and a mixture of C₆ H₁₃ CH(OH)C₁₀ H₂₀COOC₄₀ H₈₁ (Compound a, 6 mg/m²) /C₅₀ H₁₀₁ O(CH₂ CH₂ O)₁₆ H (Compound b,9 mg/m²) were coated. The mixture was prepared by melting the compoundsin xylene/propylene monomethyl ether (1/1) at 105° C. andpouring-dispersing the melt in propylene monomethyl ether (10-foldamount) at normal temperature. The resulting mixture was formed into adispersion (average particle size: 0.01 μm) in acetone and then added.Silica particles (0.3 μm) as a matting agent and alumina oxides (0.15μm) covered with 3-poly(polymerization degree:15)oxyethylenepropyloxytrimethoxysilane (15 wt %) as an abrasive eachwas added to give coverage of 15 mg/m². The drying was conducted at 115°C. for 6 minutes (rollers and the conveyance device in the drying zoneall were heated to 115° C.). The thus-provided slipping layer hadexcellent capabilities such that the coefficient of dynamic friction was0.06 (stainless steel ball: 5 mmφ; load: 100 g; speed: 6 cm/min), thecoefficient of static friction was 0.07 (by clip method) and thecoefficient of dynamic friction between the emulsion surface and theslipping layer, which will be described later, was 0.12.

4) Coating of light-sensitive layer

The layers each having the following composition were coated to overlayone on another on the side of a support opposite to the back layerprovided above to prepare a color negative film. This film wasdesignated as Sample 401.

(Composition of light-sensitive layer)

The main materials used in each layer are classified as follows.

ExC: cyan coupler

ExM: magenta coupler

ExY: yellow coupler

ExS: sensitizing dye

UV: ultraviolet absorbent

HBS: high-boiling point organic solvent

H: gelatin hardening agent

Numerals corresponding to respective components show coating amountsexpressed by the unit of g/m² and in case of silver halide, they showcoating amounts in terms of silver. With respect to sensitizing dyes,the coating amount is shown by the unit mol per mol of silver halide inthe same layer.

    ______________________________________                                        First Layer (antihalation layer)                                              Black colloidal silver                                                                             as silver                                                                              0.09                                            Gelatin                       1.60                                            ExM-1                         0.12                                            ExF-1                         2.0 × 10.sup.-3                           Solid Disperse Dye ExF-2      0.030                                           Solid Disperse Dye ExF-3      0.040                                           HBS-1                         0.15                                            HBS-2                         0.02                                            Second Layer (interlayer)                                                     Silver Iodobromide Emulsion M                                                                      as silver                                                                              0.065                                           ExC-2                         0.04                                            Polyethylacrylate latex       0.20                                            Gelatin                       1.04                                            Third Layer (low-sensitivity red-                                             sensitive emulsion laver)                                                     Silver Iodobromide Emulsion A                                                                      as silver                                                                              0.25                                            Silver Iodobromide Emulsion B                                                                      as silver                                                                              0.25                                            ExS-1                         6.9 × 10.sup.-5                           ExS-2                         1.8 × 10.sup.-5                           ExS-3                         3.1 × 10.sup.-4                           ExC-1                         0.17                                            ExC-3                         0.030                                           ExC-4                         0.10                                            ExC-5                         0.020                                           ExC-6                         0.010                                           Cpd-2                         0.025                                           HBS-1                         0.10                                            Gelatin                       0.87                                            Fourth Layer (medium-sensitivity red-                                         sensitive emulsion layer)                                                     Silver Iodobromide Emulsion C                                                                      as silver                                                                              0.70                                            ExS-1                         3.5 × 10.sup.-4                           ExS-2                         1.6 × 10.sup.-5                           ExS-3                         5.1 × 10.sup.-4                           ExC-1                         0.13                                            ExC-2                         0.060                                           ExC-3                         0.0070                                          ExC-4                         0.090                                           ExC-5                         0.015                                           ExC-6                         0.0070                                          Cpd-2                         0.023                                           HBS-1                         0.10                                            Gelatin                       0.75                                            Fifth Layer (high-sensitivity red-                                            sensitive emulsion layer)                                                     Silver Iodobromide Emulsion D                                                                      as silver                                                                              1.40                                            ExS-1                         2.4 × 10.sup.-4                           ExS-2                         1.0 × 10.sup.-4                           ExS-3                         3.4 × 10.sup.-4                           ExC-1                         0.10                                            ExC-3                         0.045                                           ExC-6                         0.020                                           ExC-7                         0.010                                           Cpd-2                         0.050                                           HBS-1                         0.22                                            HBS-2                         0.050                                           Gelatin                       1.10                                            Sixth Layer (interlayer)                                                      Cpd-1                         0.090                                           Solid Disperse Dye ExF-4      0.030                                           HBS-1                         0.050                                           Polyethylacrylate latex       0.15                                            Gelatin                       1.10                                            Seventh Layer (low-sensitivity green-                                         sensitive emulsion layer)                                                     Silver Iodobromide Emulsion E                                                                      as silver                                                                              0.15                                            Silver Iodobromide Emulsion F                                                                      as silver                                                                              0.10                                            Silver Iodobromide Emulsion G                                                                      as silver                                                                              0.10                                            ExS-4                         3.0 × 10.sup.-5                           ExS-5                         2.1 × 10.sup.-4                           ExS-6                         8.0 × 10.sup.-4                           ExM-2                         0.33                                            ExM-3                         0.086                                           ExY-1                         0.015                                           HBS-1                         0.30                                            HBS-3                         0.010                                           Gelatin                       0.73                                            Eighth Layer (medium-sensitivity green-                                       sensitive emulsion layer                                                      Silver Iodobromide Emulsion H                                                                      as silver                                                                              0.80                                            ExS-4                         3.2 × 10.sup.-5                           ExS-5                         2.2 × 10.sup.-4                           ExS-6                         8.4 × 10.sup.-4                           ExC-8                         0.010                                           ExM-2                         0.10                                            ExM-3                         0.025                                           ExY-1                         0.018                                           ExY-4                         0.010                                           ExY-5                         0.040                                           HBS-1                         0.13                                            HBS-3                         4.0 × 10.sup.-3                           Gelatin                       0.80                                            Ninth Layer (high-sensitivity green-                                          sensitive emulsion layer)                                                     Silver Iodobromide Emulsion I                                                                      as silver                                                                              1.25                                            ExS-4                         3.7 × 10.sup.-5                           ExS-5                         8.1 × 10.sup.-5                           ExS-6                         3.2 × 10.sup.-4                           ExC-1                         0.010                                           ExM-1                         0.020                                           ExM-4                         0.025                                           ExM-5                         0.040                                           Cpd-3                         0.040                                           HBS-1                         0.25                                            Polyethylacrylate latex       0.15                                            Gelatin                       1.33                                            Tenth Layer (yellow filter layer)                                             Yellow colloidal silver                                                                            as silver                                                                              0.015                                           Cpd-1                         0.16                                            Solid Disperse Dye ExF-5      0.060                                           Solid Disperse Dye ExF-6      0.060                                           Oil-Soluble Dye ExF-7         0.010                                           HBS-1                         0.60                                            Gelatin                       0.60                                            Eleventh Layer (low-sensitivity blue-                                         sensitive emulsion layer)                                                     Silver Iodobromide Emulsion J                                                                      as silver                                                                              0.09                                            Silver Iodobromide Emulsion K                                                                      as silver                                                                              0.09                                            ExS-7                         8.6 × 10.sup.-4                           ExC-8                         7.0 × 10.sup.-3                           ExY-1                         0.050                                           ExY-2                         0.22                                            ExY-3                         0.50                                            ExY-4                         0.020                                           Cpd-2                         0.10                                            Cpd-3                         4.0 × 10.sup.-3                           HBS-1                         0.28                                            Gelatin                       1.20                                            Twelfth Layer (high-sensitivity blue-                                         sensitive emulsion layer)                                                     Silver Iodobromide Emulsion L                                                                      as silver                                                                              1.00                                            ExS-7                         4.0 × 10.sup.-4                           ExY-2                         0.10                                            ExY-3                         0.10                                            EXY-4                         0.010                                           Cpd-2                         0.10                                            Cpd-3                         1.0 × 10.sup.-3                           HBS-1                         0.070                                           Gelatin                       0.70                                            Thirteenth Layer (first protective layer)                                     UV-1                          0.19                                            UV-2                          0.075                                           UV-3                          0.065                                           HBS-1                         5.0 × 10.sup.-2                           HBS-4                         5.0 × 10.sup.-2                           Gelatin                       1.8                                             Fourteenth Layer (second protective layer)                                    Silver Iodobromide Emulsion M                                                                      as silver                                                                              0.10                                            H-1                           0.40                                            B'-1 (diameter: 1.7 μm)    5.0 × 10.sup.-2                           B'-2 (diameter: 1.7 μm)    0.15                                            B'-3                          0.05                                            S-1                           0.20                                            Gelatin                       0.70                                            ______________________________________                                    

Further, in order to provide good preservability, processability,pressure durability, antimold/bactericidal property, antistatic propertyand coatability, W-1, W-2, W-3, B'-4, B'-5, B'-6, F-1, F-2, F-3, F-4,F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17,iron salt, lead salt, gold salt, platinum salt, palladium salt, iridiumsalt or rhodium salt was appropriately added to each layer.

                                      TABLE 3                                     __________________________________________________________________________              Coefficient of                                                      Average   Variation in                                                                         Average Grain Projected                                      AgI       AgI Content                                                                          Size, Sphere-                                                                        Coefficient of                                                                       Area, Circle-                                                                        Diameter/                               Content   among Grains                                                                         Corresponding                                                                        Variation in                                                                         Corresponding                                                                        Thickness                               (%)       (%)    Diameter (μm)                                                                     Grain Size (%)                                                                       Diameter (μm)                                                                     Ratio                                   __________________________________________________________________________    Emulsion A                                                                          1.7 10     0.46   15     0.56   5.5                                     Emulsion B                                                                          3.5 15     0.57   20     0.78   4.0                                     Emulsion C                                                                          8.9 25     0.66   25     0.87   5.8                                     Emulsion D                                                                          8.9 18     0.84   26     1.03   3.7                                     Emulsion E                                                                          1.7 10     0.46   15     0.56   5.5                                     Emulsion F                                                                          3.5 15     0.57   20     0.78   4.0                                     Emulsion G                                                                          8.8 25     0.61   23     0.77   4.4                                     Emulsion H                                                                          8.8 25     0.61   23     0.77   4.4                                     Emulsion I                                                                          8.9 18     0.84   26     1.03   3.7                                     Emulsion J                                                                          1.7 10     0.46   15     0.50   4.2                                     Emulsion K                                                                          8.8 18     0.64   23     0.85   5.2                                     Emulsion L                                                                          14.0                                                                              25     1.28   26     1.46   3.5                                     Emulsion M                                                                          1.0 --     0.07   15     --     1                                       __________________________________________________________________________

In Table 3:

(1) Emulsions J to L were subjected to reduction sensitization at thegrain preparation using thiourea dioxide and thiosulfonic acid accordingto the example of JP-A-2-191938 (corresponding to U.S. Pat. No.5,061,614);

(2) Emulsions A to I were subjected to gold sensitization, sulfursensitization and selenium sensitization in the presence of the spectralsensitizing dyes described in each light-sensitive layer and sodiumthiocyanate according to the example of JP-A-3-237450 (corresponding toEP-A-443453);

(3) in the preparation of tabular grains, low molecular weight gelatinwas used according to the example of JP-A-1-158426;

(4) in tabular grains, dislocation lines were observed through ahigh-pressure electron microscope as described in JP-A-3-237450(corresponding to EP-A-443453); and

(5) Emulsion L is a double structure grain containing an inner highiodide core described in JP-A-60-143331.

Preparation of Dispersion Product of Organic Solid Disperse Dye:

Solid Disperse Dye ExF-2 was dispersed as follows. That is, 21.7 ml ofwater, 3 ml of a 5% aqueous solution of sodiump-octylphenoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueoussolution of p-octylphenoxypolyoxyethylene ether (polymerization degree:10) were poured into a 700 ml-volume pot mill, then thereto 5.0 g of DyeExF-2 and 500 ml of zirconium oxide beads (diameter: 1 mm) were addedand the content was dispersed for 2 hours. In this dispersion, a BO-typevibration ball mill manufactured by Chuo Koki KK was used. After thedispersion, the content was taken out and added to 8 g of a 12.5%aqueous gelatin solution and the beads were removed by filtration toobtain a gelatin dispersion of the dye. The dye fine particles had anaverage particle size of 0.44 μm.

Solid dispersion products of ExF-3, ExF-4 and ExF-6 each was obtained inthe same manner. The average particle size of dye fine particles was0.24, 0.45 or 0.52 μm, respectively. ExF-5 was dispersed by themicroprecipitation dispersion method described in Example 1 ofEP-A-549489. The average particle size was 0.06 μm. ##STR94##

Each of the thus-prepared photographic material was cut into a size of24 mm (width)×160 cm. At the portion 0.7 mm distant from one side widthdirection in the length direction of the photographic material, twoperforations of 2 mm square were provided at a distance of 5.8 mm. Apair of two perforations was provided at a distance of 32 mm. Then, eachfilm was housed in a plastic-made film cartridge described in FIGS. 1 to7 of U.S. Pat. No. 5,296,887.

On each of these samples, FM signals were recorded from the magneticrecording layer-coated surface side between perforations at a feedingrate of 1,000/s using a head having a head gap of 5 μm and a turn numberof 2,000 and capable of inputting/outputting.

After recording of FM signals, each sample was exposed to light of 1,000cms uniformly throughout the emulsion surface and then processed by thefollowing method. Thereafter, each sample was again housed in the filmcartridge where it had been housed.

Sample 401 was cut into a width of 35 mm, used for photographing by acamera and processed in the following manner at a processing rate of 1m² /day over 15 days (running processing).

Each processing was conducted as follows using an automatic developingmachine FP-360B manufactured by Fuji Photo Film Co., Ltd. The machinewas modified so that the overflow solution of the bleaching bath did notflow into the post-bath but all was discharged to the waste water tank.On this FP-360B, an evaporation correcting means described in JIIIJournal of Technical Disclosure, No. 94-4992 was mounted.

The processing steps and the composition of each processing solution aredescribed below.

    ______________________________________                                        (Processing Step)                                                                                  Processing                                                                              Replenish-                                                                            Tank                                              Process-  Temperature                                                                             ing Amount*                                                                           Volume                                 Step       ing Time  (°C.)                                                                            (ml)    (l)                                    ______________________________________                                        Color development                                                                        3 min 5 sec                                                                             38.0      20      17                                     Bleaching  50 sec    38.0      5       5                                      Fixing (1) 50 sec    38.0      --      5                                      Fixing (2) 50 sec    38.0      8       5                                      Water washing                                                                            30 sec    38.0      17      3.5                                    Stabilization (1)                                                                        20 sec    38.0      --      3                                      Stabilization (2)                                                                        20 sec    38.0      15      3                                      Drying     1 min 30 sec                                                                            60                                                       ______________________________________                                         *Replenishing amount was per 1.1 m of the 35 mmwidth photographic materia     (corresponding to 1 roll of 24 Ex.).                                     

The stabilizing solution was in a countercurrent system of from (2) to(1) and the overflow solution of washing water was all introduced intothe fixing (2). The fixing solution was also flown from (2) to (1)connected by countercurrent piping. The carried-over amounts ofdeveloper into the bleaching step, of bleaching solution into the fixingstep, of fixing solution into the water washing step were 2.5 ml, 2.0 mland 2.0 ml, respectively, per 1.1 m of the 35 mm-width photographicmaterial. The cross-over time was 6 seconds in each interval and thistime is included in the processing time of the previous step.

The open area of the above-described processing machine was 100 cm² forthe color developer, 120 cm² for the bleaching solution and about 100cm² for other processing solutions.

The composition of each processing solution is shown below.

    ______________________________________                                                         Tank                                                                          Solution                                                                              Replenisher                                                           (g)     (g)                                                  ______________________________________                                        (Color Developer)                                                             Diethylenetriaminepentaacetic                                                                    2.0       2.0                                              acid                                                                          1-Hydroxyethylidene-1,1-                                                                         2.0       2.0                                              diphosphonic acid                                                             Sodium sulfite     3.9       5.3                                              Potassium carbonate                                                                              37.5      39.0                                             Potassium bromide  1.4       0.4                                              Potassium iodide     1.3 mg  --                                               Disodium N,N-bis(2-sulfonato-                                                                    2.0       2.0                                              ethyl)hydroxylamine                                                           Hydroxylamine sulfate                                                                            2.4       3.3                                              2-Methyl-4- N-ethyl-N-(β-                                                                   4.5       6.4                                              hydroxyethyl)amino!aniline                                                    sulfate                                                                       Water to make        1.0 l     1.0 l                                          PH (adjusted by potassium                                                                        10.05     10.18                                            hydroxide and sulfuric acid)                                                  (Bleaching Solution)                                                          Ammonium 1,3-diamino-                                                                             118     180                                               propanetetraacetato ferrate                                                   monohydrate                                                                   Ammonium bromide    80      115                                               Ammonium nitrate    14      21                                                Succinic acid       40      60                                                Maleic acid         33      50                                                Water to make         1.0 l   1.0 l                                           pH (adjusted by aqueous ammonia)                                                                  4.4     4.0                                               (Fixing Solution)                                                             Ammonium methanesulfinate                                                                         10      30                                                Ammonium methanethiosulfonate                                                                     4       12                                                Aqueous solution of ammonium                                                                      280 ml  840 ml                                            thiosulfate (700 g/l)                                                         Imidazole           7       20                                                Ethylenediaminetetraacetic acid                                                                   15      45                                                Water to make         1.0 l   1.0 l                                           pH (adjusted by aqueous ammonia                                                                   7.4     7.45                                              and acetic acid)                                                              ______________________________________                                    

(Washing Water)

Tap water was passed through a mixed bed column filled with an H-typestrongly acidic cation exchange resin (Amberlite IR-120B, produced byRhom and Haas) and an OH-type strongly basic anion exchange resin(Amberlite IR-400, produced by the same company) to reduce the calciumand magnesium ion concentrations each to 3 mg/l or less and then thereto20 mg/l of sodium isocyanurate dichloride and 150 mg/l of sodium sulfatewere added. The resulting solution had a pH of from 6.5 to 7.5.

(Stabilizing Solution)

The tank solution and the replenisher were common.

    ______________________________________                                                              (unit: g)                                               ______________________________________                                        Sodium p-toluenesulfinate                                                                             0.03                                                  Polyoxyethylene-p-monononylphenyl ether                                                               0.2                                                   (average polymerization degree: 10)                                           Disodium ethylenediaminetetraacetate                                                                  0.05                                                  1,2,4-Triazole          1.3                                                   1,4-Bis(1,2,4-triazol-1-ylmethyl)-                                                                    0.75                                                  piperazine                                                                    1,2-Benzoisothiazolin-3-one                                                                           0.10                                                  Water to make           1.0 l                                                 pH                      8.5                                                   ______________________________________                                    

EXAMPLE 5

Samples were prepared by adding Compound A-1, A-4, A-16, A-23 or A-33for use in the present invention in an amount of 1.5×10⁻² mol/mol-Ag tothe fourth, fifth and sixth layers of Sample 101 in Example 1 ofJP-A-6-118533. Each sample was exposed and then allowed to stand underforcedly deteriorating conditions of 50° C. and 60% for 7 days.Thereafter, each sample was subjected to color reversal processingdescribed in JP-A-6-118533 (pages 37 and 38) and evaluated. As a result,the photographic materials to which the compound for use in the presentinvention was added, exhibited advantageous capability such that theincrease in the sensitivity upon leaving after exposure was small andthe reduction in the maximum color density was small, as compared withthe photographic material to which the compound was not added.

EXAMPLE 6

Preparation of Emulsion A

To 1 l of water, 25 g of potassium bromide, 15 g of potassium iodide,1.9 g of potassium thiocyanate and 24 g of gelatin were added. Thevessel containing the mixture was kept at a temperature of 60° C. andthereto, an aqueous silver nitrate solution and an aqueous potassiumbromide solution were added by a double jet method according to a usualammonia method while vigorously stirring to thereby prepare a thickplaty silver iodobromide emulsion having an iodide content of 10 mol %and an average grain size of 1.0 μm and relatively close to amorphousgrain. Thereafter, the temperature was lowered to 35° C. and solublesalts were removed by a coagulation-flocculation method. Then, thetemperature was elevated to 40° C., 82 g of gelatin was added and the pHand the pAg were adjusted to 6.40 and 8.80, respectively, by causticsoda and sodium bromide.

After elevating the temperature to 61° C., 0.95 g of 2-phenoxyethanolwas added and further 213 mg of Sensitizing Dye-A shown below was added.After 10 minutes, 1.2 mg of sodium thiosulfate pentahydrate, 28 mg ofpotassium thiocyanate and 0.4 mg of chloroauric acid were added andafter 65 minutes, the mixture was rapidly cooled and solidified.##STR95## Preparation of Emulsion B

To 1 l of water, 25 g of potassium bromide, 9 g of potassium iodide, 7.6g of potassium thiocyanate and 24 g of gelatin were added. The vesselcontaining the mixture was kept at a temperature of 40° C. and thereto,an aqueous silver nitrate solution and an aqueous potassium bromidesolution were added by a double jet method according to a usual ammoniamethod while vigorously stirring to thereby prepare a thick platy silveriodobromide emulsion having an iodide content of 6 mol % and an averagegrain size of 0.6 μm and relatively close to amorphous grain.Thereafter, the temperature was lowered to 35° C. and soluble salts wereremoved by a coagulation-flocculation method. Then, the temperature waselevated to 40° C., 110 g of gelatin was added and the pH and the pAgwere adjusted to 6.60 and 8.90, respectively, by caustic soda and sodiumbromide. After elevating the temperature to 56° C., 0.8 mg ofchloroauric acid, 9 mg of potassium thiocyanate and 4 mg of sodiumthiosulfate were added. After 55 minutes, 180 mg of Dye-A was added.After 10 minutes, the mixture was rapidly cooled and solidified.

Preparation of Coated Samples

Coated Sample 601 was prepared according to the production methoddescribed in JP-A-62-115035 by coating the following layers on atriacetyl cellulose support of which emulsion coating surface waspreviously subbed and back surface was coated by:

    ______________________________________                                        Compound-I                60 mg/m.sup.2,                                      Diacetyl cellulose        143 mg/m.sup.2,                                     Silicon oxide             5 mg/m.sup.2, and                                   Compound-I                                                                     ##STR96##                                                                    First Layer (antihalation layer)                                              Gelatin                   1.0 g/m.sup.2                                       Compound-II               140 mg/m.sup.2                                      Compound-III              15 mg/m.sup.2                                       Dye-I                     26 mg/m.sup.                                        Dye-II                    16 mg/m.sup.2                                       Compound-II                                                                    ##STR97##                                                                    Compound-III                                                                   ##STR98##                                                                    Dye-I                                                                          ##STR99##                                                                    Dye-II                                                                         ##STR100##                                                                   Second Layer (interlayer)                                                     Gelatin                   0.4 g/m.sup.2                                       Polypotassium-p-vinylbenzene sulfonate                                                                  5 mg/m.sup.2                                        Third Layer (emulsion layer)                                                  Emulsion B as silver      1.36 g/m.sup.2                                      Gelatin                   2.0 g/m.sup.2                                       4-Hydroxy-6-methyl-1,3,3a,7-tetraazaindene                                                              15 mg/m.sup.2                                       C.sub.18 H.sub.35 O(CH.sub.2 CH.sub.2 O).sub.25 H                                                       10 mg/m.sup.2                                       Compound-IV               1.5 mg/m.sup.2                                      Polypotassium-p-vinylbenzene sulfonate                                                                  50 mg/m.sup.2                                       Bis(vinylsulfonylacetamido)ethane                                                                       65 mg/m.sup.2                                       Compound-IV                                                                    ##STR101##                                                                   Fourth Layer (emulsion layer)                                                 Emulsion A as silver      4.2 g/m.sup.2                                       Gelatin                   6.5 g/m.sup.2                                       Dextran (average molecular weight: 150,000)                                                             1.2 g/m.sup.2                                       4-Hydroxy-6-methyl-1,3,3a,7-tetraazaindene                                                              41 mg/m.sup.2                                       C.sub.18 H.sub.35 O(CH.sub.2 CH.sub.2 O).sub.25 H                                                       23 mg/m.sup.2                                       Trimethylolpropane        500 mg/m.sup.2                                      Polypotassium-p-vinylbenzene sulfonate                                                                  88 mg/m.sup.2                                       Polyacrylic acid          54 mg/m.sup.2                                       Fifth Layer (surface protective layer)                                        Gelatin                   0.8 g/m.sup.2                                       Compound-V                13 mg/m.sup.2                                       Compound-VI               50 mg/m.sup.2                                       Compound-VII              1.8 mg/m.sup.2                                      Polypotassium-p-vinylbenzene sulfonate                                                                  6 mg/m.sup.2                                        Polymethyl methacrylate fine particles                                                                  24 mg/m.sup.2                                       (average particle size: 3 μm)                                              Compound-VIII             50 mg/m.sup.2                                       Compound-V                                                                     ##STR102##                                                                   Compound-VI                                                                    ##STR103##                                                                   Compound-VII                                                                   ##STR104##                                                                   Compound-VIII                                                                  ##STR105##                                                                   W-1                                                                            ##STR106##                                                                   Solv-1                                                                         ##STR107##                                                                   ______________________________________                                    

To 300 ml of ethyl acetate, 18.9 g of Compound A-1 for use in thepresent invention, 19.0 g of poly-t-butylacrylamido (molecular weight:100,000), 9.5 g of high boiling point organic solvent (Solv-1) and 38.0g of surface active agent (W-1) were added and dissolved under heating.The resulting solution was added to a 10% aqueous gelatin solution andemulsion-dispersed in a house-use mixer for 10 minutes.

The emulsified product obtained was added to the third and fourth layersof Sample 601 so that the coverage of Compound A-1 for use in thepresent invention could be 0.1 mol/mol-Ag, to thereby prepare Sample603. Sample 602 was prepared by removing only Compound A-1 for use inthe present invention from the emulsified product of Sample 603 andSample 604 was prepared by using Compound A-33 in place of Compound A-1for use in the present invention in Sample 603.

These samples were stored under temperature and humidity conditions of30° C. and 65% RH for 14 days after the coating. Each sample was testedaccording to the following method.

(1) Measurement of Sensitivity

Each sample was exposed through an optical wedge for 1/100 second usinga tungsten light source having a color temperature of 2854K of whichcolor temperature was increased through a color temperature variationfilter to 5400K.

Then, each sample was subjected to development, fixing, water washingand drying in an automatic developing machine. The sensitivity of eachsample is shown by a logarithm of the reciprocal of an exposure amountrequired to give an optical density 0.5 higher than the fog.

The development conditions are as follows.

    ______________________________________                                                 Processing Solution                                                                       Temperature                                                                              Time                                          ______________________________________                                        Development                                                                              HPD           26.5° C.                                                                          55 sec.                                   Fixing     Super Fujix DP2                                                                             26.5° C.                                                                          76 sec.                                   Water washing                                                                            Flowing water 20° C.                                                                            95 sec.                                   Drying                   50° C.                                                                            69 sec.                                   ______________________________________                                    

The aging stability of photographic property when the photographicmaterial was allowed to stand after photographing was evaluatedaccording to the following method.

Samples 601 to 604 were exposed by the above-described method and thenallowed to stand under conditions of 50° C. and 60% RH for 7 days. Then,each sample was processed and measured according to the method describedabove. The results are shown in Table 4 as a relative value to that ofthe sample processed immediately after exposure. The nearer to 0 thevalue is, the smaller the change due to aging is.

                  TABLE 4                                                         ______________________________________                                                          Aging Stability                                                               after Photographing                                                                 Change in                                                                              Increase                                     Sample     Compound     Sensitivity                                                                            of Fog                                       ______________________________________                                        601        --           +0.06    0.04                                         (Comparison)                                                                  602        --           +0.06    0.04                                         (Comparison)                                                                  603        A-1          +0.01    0.01                                         (Invention)                                                                   604        A-33         +0.01    0.01                                         (Invention)                                                                   ______________________________________                                    

It is clearly seen from Table 4 that the photographic materialscontaining the compound for use in the present invention wereoutstandingly improved in the aging stability of the photographicproperty when they were left after photographing.

EXAMPLE 7

Sample 701 as a multi-layer color photographic material was prepared tohave layers each having the following composition, on a cellulosetriacetate film support subjected to undercoating.

Composition of Light-Sensitive Layer

The coating amounts are expressed, in the case of silver halide andcolloid silver, by the unit of g/m² of silver, in the case of couplers,additives and gelatin, by the unit of g/m² and, in the case ofsensitizing dyes, by molar number per mol of silver halide in the samelayer. The symbols used for additives have the following meanings. Whenthe additive has a plurality of effects, one of the effects is used as arepresentative.

    ______________________________________                                               UV: ultraviolet absorbent,                                                    Solv: high boiling point organic solvent                                      ExF: dye                                                                      ExS: sensitizing dye                                                          ExC: cyan coupler                                                             ExM: magenta coupler                                                          ExY: yellow coupler                                                           Cpd: additive                                                          First Layer (antihalation layer)                                              Black colloidal silver         0.15                                           Gelatin                        2.33                                           UV-1                           1.9 × 10.sup.-2                          UV-2                           4.7 × 10.sup.-2                          UV-3                           8.6 × 10.sup.-2                          ExF-3                          5.0 × 10.sup.-3                          ExM-3                          2.3 × 10.sup.-2                          Solv-1                         0.16                                           Solv-2                         0.10                                           Second Layer (interlayer)                                                     Gelatin                        0.88                                           Polyethylacrylate latex        2.6 × 10.sup.-1                          ExC-7                          5.0 × 10.sup.-2                          Third Layer (low-sensitivity red-                                             sensitive emulsion layer)                                                     Silver Iodobromide Emulsion A                                                                       as silver                                                                              0.24                                           Silver Iodobromide Emulsion B                                                                       as silver                                                                              0.65                                           Gelatin                        1.75                                           ExS-1                          6.9 × 10.sup.-4                          ExS-2                          4.0 × 10.sup.-4                          ExS-5                          6.7 × 10.sup.-4                          ExS-7                          1.4 × 10.sup.-5                          ExC-1                          3.0 × 10.sup.-1                          ExC-5                          2.0 × 10.sup.-1                          ExC-9                          2.2 × 10.sup.-2                          Cpd-4                          5.3 × 10.sup.-2                          ExC-4                          6.1 × 10.sup.-2                          Fourth Layer (medium-sensitivity red-                                         sensitive emulsion layer)                                                     Silver Iodobromide Emulsion C                                                                       as silver                                                                              0.67                                           Gelatin                        0.94                                           ExS-1                          3.5 × 10.sup.-4                          ExS-2                          2.0 × 10.sup.-4                          ExS-5                          3.4 × 10.sup.-4                          ExS-7                          6.9 × 10.sup.-6                          ExC-1                          1.3 × 10.sup.-1                          ExC-4                          4.6 × 10.sup.-2                          ExC-5                          8.6 × 10.sup.-2                          ExC-6                          1.1 × 10.sup.-2                          ExC-7                          4.6 × 10.sup.-2                          Cpd-4                          2.1 × 10.sup.-2                          Fifth Layer (high-sensitivity red-                                            sensitive emulsion layer)                                                     Silver Iodobromide Emulsion D                                                                       as silver                                                                              0.67                                           Gelatin                        0.68                                           ExS-1                          3.2 × 10.sup.-4                          ExS-2                          1.8 × 10.sup.-4                          ExS-5                          3.1 × 10.sup.-4                          ExS-7                          4.8 × 10.sup.-5                          ExC-1                          5.1 × 10.sup.-2                          ExC-6                          9.0 × 10.sup.-3                          ExC-4                          2.0 × 10.sup.-2                          ExC-9                          1.0 × 10.sup.-2                          Cpd-4                          2.1 × 10.sup.-3                          Solv-1                         0.08                                           Solv-2                         0.04                                           Sixth Layer (interlayer)                                                      Gelatin                        0.62                                           Cpd-1                          0.08                                           Polyethylacrylate latex        4.1 × 10.sup.-2                          Solv-1                         4.0 × 10.sup.-2                          Seventh Layer (low-sensitivity green-                                         sensitive emulsion layer)                                                     Silver Iodobromide Emulsion E                                                                       as silver                                                                              0.14                                           Gelatin                        0.49                                           ExS-8                          5.7 × 10.sup.-5                          ExS-4                          9.0 × 10.sup.-4                          ExS-5                          1.8 × 10.sup.-4                          ExM-1                          0.26                                           Solv-1                         0.15                                           Solv-3                         7.0 × 10.sup.-3                          Eighth Layer (medium-sensitivity green-                                       sensitive emulsion layer)                                                     Silver Iodobromide Emulsion F                                                                       as silver                                                                              0.08                                           Silver Iodobromide Emulsion E                                                                       as silver                                                                              0.01                                           Gelatin                        0.14                                           ExS-8                          4.3 × 10.sup.-5                          ExS-4                          6.8 × 10.sup.-4                          ExS-5                          1.3 × 10.sup.-4                          ExM-1                          4.9 × 10.sup.-2                          ExM-7                          1.0 × 10.sup.-2                          ExY-1                          5.0 × 10.sup.-3                          Solv-1                         3.3 × 10.sup.-2                          Solv-3                         1.5 × 10.sup.-3                          Ninth Layer (high-sensitivity green-                                          sensitive emulsion layer)                                                     Silver Iodobromide Emulsion G                                                                       as silver                                                                              0.60                                           Gelatin                        0.60                                           ExS-4                          5.0 × 10.sup.-4                          ExS-5                          9.9 × 10.sup.-5                          ExS-8                          3.2 × 10.sup.-5                          ExM-7                          2.4 × 10.sup.-2                          ExM-1                          8.4 × 10.sup.-2                          ExY-1                          6.7 × 10.sup.-2                          ExC-1                          6.0 × 10.sup.-3                          ExC-4                          8.0 × 10.sup.-3                          Cpd-6                          8.0 × 10.sup.-3                          Solv-1                         0.12                                           Solv-2                         0.06                                           Solv-3                         6.0 × 10.sup.-3                          Tenth Layer (interlayer)                                                      Gelatin                        0.39                                           UV-2                           1.4 × 10.sup.-2                          UV-3                           1.6 × 10.sup.-2                          UV-5                           4.2 × 10.sup.-2                          Cpd-1                          2.6 × 10.sup.-2                          Polyethylacrylate latex        1.4 × 10.sup.-2                          Solv-1                         2.8 × 10.sup.-2                          Eleventh Layer (donor layer having interlayer                                 effect to red-sensitive layer)                                                Silver Iodobromide Emulsion H                                                                       as silver                                                                              1.12                                           Silver Iodobromide Emulsion I                                                                       as silver                                                                              0.26                                           Gelatin                        1.61                                           ExS-3                          6.4 × 10.sup.-4                          ExM-2                          2.7 × 10.sup.-2                          ExM-1                          2.0 × 10.sup.-1                          ExM-7                          1.7 × 10.sup.-1                          ExY-2                          2.0 × 10.sup.-1                          Solv-1                         0.50                                           Twelfth Layer (yellow filter layer)                                           Yellow colloidal silver        3.3 × 10.sup.-2                          Gelatin                        0.61                                           Cpd-1                          4.3 × 10.sup.-2                          Cpd-2                          7.9 × 10.sup.-2                          Cpd-5                          1.0 × 10.sup.-3                          Solv-1                         4.7 × 10.sup.-2                          Thirteenth Layer (low-sensitivity blue-                                       sensitive emulsion layer                                                      Silver Iodobromide Emulsion J                                                                       as silver                                                                              0.62                                           Gelatin                        1.67                                           ExS-9                          8.8 × 10.sup.-4                          ExY-2                          1.2 × 10.sup.-1                          ExY-3                          5.5 × 10.sup.-1                          ExC-9                          6.3 × 10.sup.-2                          ExY-7                            2 × 10.sup.-2                          ExY-8                            1 × 10.sup.-2                          ExC-1                          3.0 × 10.sup.-2                          ExC-10                         8.4 × 10.sup.-2                          Solv-1                         0.33                                           Fourteenth Layer (high-sensitivity blue-                                      sensitive emulsion layer)                                                     Silver Iodobromide Emulsion K                                                                       as silver                                                                              0.14                                           Silver Iodobromide Emulsion L                                                                       as silver                                                                              0.10                                           Silver Iodobromide Emulsion M                                                                       as silver                                                                              0.22                                           Gelatin                        1.00                                           ExS-6                          4.4 × 10.sup.-4                          ExY-2                          7.6 × 10.sup.-2                          ExY-3                          1.1 × 10.sup.-1                          ExY-6                          3.1 × 10.sup.-1                          ExY-8                            4 × 10.sup.-2                          ExC-1                          1.8 × 10.sup.-2                          ExC-10                         2.3 × 10.sup.-2                          Solv-1                         1.7 × 10.sup.-1                          Fifteenth Layer (first protective layer)                                      Fine Grain Silver     as silver                                                                              0.06                                           Iodobromide Emulsion N                                                        Gelatin                        0.51                                           UV-2                           4.0 × 10.sup.-2                          UV-3                           4.9 × 10.sup.-2                          UV-5                           0.12                                           Cpd-3                          0.10                                           ExF-4                          2.1 × 10.sup.-3                          ExF-5                          6.3 × 10.sup.-3                          Solv-4                         2.0 × 10.sup.-2                          Polyethylacrylate latex        9.0 × 10.sup.-2                          Sixteenth Layer (second protective layer)                                     Fine Grain Silver     as silver                                                                              0.18                                           Iodobromide Emulsion N                                                        Gelatin                        0.84                                           B'-1 (diameter: 2.0 μm)     8.0 × 10.sup.-2                          B'-2 (diameter: 2.0 μm)     8.0 × 10.sup.-2                          B'-3                           3.5 × 10.sup.-2                          W-5                            1.8 × 10.sup.-2                          H-1                            0.18                                           ______________________________________                                    

To the thus-prepared sample, 1,2-benzoisothiazolin-3-one (200 ppm onaverage to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm onaverage to gelatin) and 2-phenoxyethanol (about 10,000 ppm on average togelatin) were additionally added. Further, in order to provide goodpreservability, processability, pressure durability,antimold/bactericidal property, antistatic property and coatability,W-1, W-2, W-3, W-4, W-5, W-6, B'-1, B'-2, B'-3, B'-4, B'-5, B'-6, F-1,F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14,F-15, F-16, F-17, iron salt, lead salt, gold salt, platinum salt,iridium salt or rhodium salt was appropriately added to each layer.

Emulsions A to N used in Sample 701 were the same as Emulsions A to Nused in Sample 101 of Example 1.

The chemical formulae of additives used in Sample 701 were the same asthe chemical formulae of additives used in Sample 101 of Example 1.

To the fourth layer of Sample 701, the compound represented by formula(IB) or a comparative compound, coemulsified with the coupler in thislayer, was added to give the coated amount of 5×10⁻² mol per mol of Agin this layer. With respect to other conditions, the preparation methodof Sample 701 was followed to prepare other samples as shown in Table 6.

Evaluation on the fluctuation in the photographic property afterphotographing until processing was performed in the following manner.

Each photographic material sample was exposed for sensitometry, storedfor 3 days under forcedly deteriorating conditions of 60° C. and 60% orof 50° C. and 80%, and then subjected to the following color developmentprocessing at 38° C. The processed samples were measured on the densitythrough a red filter and a blue filter. The degree of difference in thesensitivity between these samples and the sample subjected todevelopment processing immediately after exposure was evaluated.##STR108##

Each of the color photographic materials was exposed as above and thenprocessed according to the following method.

    ______________________________________                                        Processing Method                                                                                        Processing                                                                    Temperature                                        Step           Processing Time                                                                           (°C.)                                       ______________________________________                                        Color development                                                                            3 min. 15 sec.                                                                            38                                                 Bleaching      3 min. 00 sec.                                                                            38                                                 Water washing  30 sec.     24                                                 Fixing         3 min. 00 sec.                                                                            38                                                 Water washing (1)                                                                            30 sec.     24                                                 Water washing (2)                                                                            30 sec.     24                                                 Stabilization  30 sec.     38                                                 Drying         4 min. 20 sec.                                                                            55                                                 ______________________________________                                    

The composition of each processing solution is shown below.

    ______________________________________                                                             (unit: g)                                                ______________________________________                                        (Color Developer)                                                             Diethylenetriaminepentaacetic acid                                                                   1.0                                                    1-Hydroxyethylidene-1,1-diphosphonic                                                                 2.0                                                    acid                                                                          Sodium sulfite         4.0                                                    Potassium carbonate    30.0                                                   Potassium bromide      1.4                                                    Potassium iodide       1.5 mg                                                 Hydroxylamine sulfate  2.4                                                    4- N-Ethyl-N-(β-hydroxyethyl)amino!-2-                                                          4.5                                                    methylaniline sulfate                                                         Water to make          1.0 liter                                              pH (adjusted by potassium hydroxide and                                                              10.05                                                  sulfuric acid)                                                                (Bleaching Solution)                                                          N-(2-Carboxyphenyl)iminodiacetato                                                                    25.0                                                   ferrate pentahydrate                                                          Ammonium 1,3-diaminopropanetetraacetato                                                              25.0                                                   ferrate dihydrate                                                             1,3-Diaminopropanetetraacetic acid                                                                   2.0                                                    Malonic acid           7.0                                                    Succinic acid          60.0                                                   Glutaric acid          15.0                                                   Sodium bromide         40.0                                                   Sodium nitrate         30.0                                                   Sodium hydroxide       30.0                                                   Diethanolamine         20.0                                                   Water to make          1.0 liter                                              pH (adjusted by sodium hydroxide and                                                                 4.2                                                    nitric acid)                                                                  (Fixing Solution)                                                             1,3-Diaminopropanetetraacetic acid                                                                   6.0                                                    Ammonium sulfite       20.0                                                   Ammonium thiosulfate   270.0 ml                                               (aq. soln. 750 g/l)                                                           Acetic acid (90%)      5.0                                                    Water to make          1.0 liter                                              pH (adjusted by aqueous ammonia and                                                                  6.4                                                    acetic acid)                                                                  (Stabilizing Solution)                                                        p-Nonylphenoxypolyglycidol                                                                           0.2                                                    (glycidol average polymerization                                              degree: 10)                                                                   Ethylenediaminetetraacetic acid                                                                      0.05                                                   1,2,4-Triazole         1.3                                                    1,4-Bis(1,2,4-triazol-1-ylmethyl)-                                                                   0.75                                                   piperazine                                                                    Hydroxyacetic acid     0.02                                                   Hydroxyethyl cellulose (HEC SP-2000,                                                                 0.1                                                    produced by Daicel Chemical KK)                                               1,2-Benzoisothiazolin-3-one                                                                          0.05                                                   Water to make          1.0 liter                                              pH                     8.5                                                    ______________________________________                                    

The sensitivity as a photographic property is shown by a logarithm ofthe reciprocal of an exposure amount required to give an optical density1.0 higher than the fog. The fluctuation in the photographic propertyafter photographing until processing is shown by a relative sensitivity(difference in logarithms) of the sensitivity of photographic materialsstored after exposure under forcedly deteriorating conditions to thesensitivity of the photographic material processed immediately afterexposure. The nearer to 0 the value is, the smaller the fluctuation inthe photographic property is and the more preferable the material is.

Fluctuation in the photographic property both of the red-sensitive layerto which the compound of formula (IB) was added and of theblue-sensitive layer to which the compound was not added was evaluated.When the compound of formula (IB) or a comparative compound was added,the photographic property of the blue-sensitive layer changed ascompared with the material (Sample 701) to which the compound was notadded. This reveals that the compound disadvantageously diffused fromthe red-sensitive layer (layer to which the compound was added) to theblue-sensitive layer (layer to which the compound was not added).

The results are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                        Fluctuation in Photographic                                                   Property due to Aging after                                                   Photographing until Processing                                                                       Red-Sensitive                                                                            Blue-Sensitive                                                     Layer      Layer                                       Sample       Compound  60° C., 60%                                                                       60° C., 60%                          ______________________________________                                        701 (Comparison)                                                                           --        0.20       -0.02                                       702 (Comparison)                                                                           A         0.19       -0.01                                       703 (Comparison)                                                                           B         0.20       -0.02                                       704 (Comparison)                                                                           C         0.14       -0.03                                       705 (Comparison)                                                                           D         0.14       -0.02                                       706 (Comparison)                                                                           E         0.08       -0.05                                       707 (Invention)                                                                            B-1       0.04       -0.02                                       708 (Invention)                                                                            B-2       0.03       -0.02                                       709 (Invention)                                                                            B-6       0.03       -0.02                                       710 (Invention)                                                                            B-7       0.05       -0.02                                       711 (Invention)                                                                            B-11      0.03       -0.02                                       712 (Invention)                                                                            B-18      0.03       -0.02                                       713 (Invention)                                                                            B-25      0.03       -0.02                                       714 (Invention)                                                                            B-31      0.04       -0.02                                       715 (Invention)                                                                            B-38      0.05       -0.02                                       716 (Invention)                                                                            B-40      0.01       -0.02                                       717 (Invention)                                                                            B-51      0.02       -0.02                                       718 (Invention)                                                                            B-42      0.01       -0.02                                       719 (Invention)                                                                            B-44      0.02       -0.02                                       ______________________________________                                    

As clearly seen from Table 5, the photographic materials using thecompound of formula (IB) for use in the present invention showed goodresults such that fluctuation in the photographic property due to agingafter photographing until processing of the layer to which the compoundwas added (red-sensitive layer) was small and at the same time,fluctuation due to aging of the layer to which the compound was notadded (blue-sensitive layer) was not worsened.

The compound of formula (IB) for use in the present invention affectedneither other photographic properties nor storability of the layer towhich the compound was not added.

EXAMPLE 8

Other than the compounds shown in Table 5 of Example 7, using CompoundB-3, B-4, B-5, B-8, B-9, B-10, B-12, B-13, B-14, B-15, B-16, B-17, B-19,B-20, B-21, B-22, B-23, B-24, B-26, B-27, B-28, B-29, B-30, B-32, B-33,B-34, B-35, B-36 or B-37 for use in the present invention, evaluationwas conducted. As a result, these compounds provided advantageousresults such that the change in the photographic property due to agingwas reduced when the materials were allowed to stand afterphotographing.

EXAMPLE 9

When the compound for use in the present invention was used in thegreen-sensitive layer or the blue-sensitive layer, similarly to Example7, good results were provided such that the storability of the layer towhich the compound was added was improved and the layer to which thecompound was not added was not affected.

EXAMPLE 10

1) Support

The support used in this example was prepared in the same manner as inExample 4.

2) Coating of undercoat layer

The support obtained above was subjected to discharge treatments, coatedby an undercoating solution and dried, in the same manner as in Example4.

3) Coating of back layer

On one surface of the undercoated support, an antistatic layer, amagnetic recording layer and a slipping layer were coated as a backlayer in the same manner as in Example 4. The slipping layer had thesame property as that of Example 4.

4) Coating of light-sensitive layer

The layers each having the following composition were coated to overlayone on another on the side of a support opposite to the back layerprovided above to prepare a color negative film. This film wasdesignated as Sample 1001.

(Composition of light-sensitive layer)

The main materials used in each layer are classified as follows.

ExC: cyan coupler

ExM: magenta coupler

ExY: yellow coupler

ExS: sensitizing dye

UV: ultraviolet absorbent

HBS: high-boiling point organic solvent

H: gelatin hardening agent

Numerals corresponding to respective components show coating amountsexpressed by the unit of g/m² and in case of silver halide, they showcoating amounts in terms of silver. With respect to sensitizing dyes,the coating amount is shown by the unit mol per mol of silver halide inthe same layer.

    ______________________________________                                        First Layer (antihalation layer)                                              Black colloidal silver  as silver                                                                             0.09                                          Gelatin                         1.60                                          ExM-1                           0.12                                          ExF-1                           2.0 × 10.sup.-3                         Solid Disperse Dye ExF-2        0.030                                         Solid Disperse Dye ExF-3        0.040                                         HBS-1                           0.15                                          HBS-2                           0.02                                          Second Layer (interlayer)                                                     Silver Iodobromide Emulsion M                                                                         as silver                                                                             0.065                                         ExC-2                           0.04                                          Polyethylacrylate latex         0.20                                          Gelatin                         1.04                                          Third Layer (low-sensitivity red-sensitive                                    emulsion layer)                                                               Silver Iodobromide Emulsion A                                                                         as silver                                                                             0.30                                          Silver Iodobromide Emulsion B                                                                         as silver                                                                             0.20                                          ExS-1                           6.9 × 10.sup.-5                         ExS-2                           1.8 × 10.sup.-5                         ExS-3                           3.1 × 10.sup.-4                         ExC-1                           0.17                                          ExC-3                           0.030                                         ExC-4                           0.10                                          ExC-5                           0.020                                         ExC-6                           0.010                                         Cpd-2                           0.025                                         HBS-1                           0.15                                          Gelatin                         0.87                                          Fourth Layer (medium-sensitivity red-sensitive                                emulsion layer)                                                               Silver Iodobromide Emulsion C                                                                         as silver                                                                             0.70                                          ExS-1                           3.5 × 10.sup.-4                         ExS-2                           1.6 × 10.sup.-5                         ExS-3                           5.1 × 10.sup.-4                         ExC-1                           0.13                                          ExC-2                           0.060                                         ExC-3                           0.0070                                        ExC-4                           0.090                                         ExC-5                           0.015                                         ExC-6                           0.0070                                        Cpd-2                           0.023                                         HBS-1                           0.08                                          Gelatin                         0.75                                          Fifth Layer (high-sensitivity red-sensitive emulsion                          layer)                                                                        Silver Iodobromide Emulsion D                                                                         as silver                                                                             1.20                                          ExS-1                           2.4 × 10.sup.-4                         ExS-2                           1.0 × 10.sup.-4                         ExS-3                           3.4 × 10.sup.-4                         ExC-1                           0.10                                          ExC-3                           0.045                                         ExC-6                           0.020                                         ExC-7                           0.010                                         Cpd-2                           0.050                                         HBS-1                           0.22                                          HBS-2                           0.050                                         Gelatin                         1.10                                          Sixth Layer (interlayer)                                                      Cpd-1                           0.090                                         Solid Disperse Dye ExF-4        0.030                                         HBS-1                           0.050                                         Polyethylacrylate latex         0.15                                          Gelatin                         1.10                                          Seventh Layer (low-sensitivity green-sensitive                                emulsion layer)                                                               Silver Iodobromide Emulsion E                                                                         as silver                                                                             0.10                                          Silver Iodobromide Emulsion F                                                                         as silver                                                                             0.15                                          Silver Iodobromide Emulsion G                                                                         as silver                                                                             0.10                                          ExS-4                           3.0 × 10.sup.-5                         ExS-5                           2.1 × 10.sup.-4                         ExS-6                           8.0 × 10.sup.-4                         ExM-2                           0.33                                          ExM-3                           0.086                                         ExY-l                           0.015                                         HBS-1                           0.30                                          HBS-3                           0.010                                         Gelatin                         0.73                                          Eighth Layer (medium-sensitivity green-sensitive                              emulsion layer                                                                Silver Iodobromide Emulsion H                                                                         as silver                                                                             0.80                                          ExS-4                           3.2 × 10.sup.-5                         ExS-5                           2.2 × 10.sup.-4                         ExS-6                           8.4 × 10.sup.-4                         ExC-8                           0.010                                         ExM-2                           0.10                                          ExM-3                           0.025                                         ExY-1                           0.018                                         ExY-4                           0.010                                         ExY-5                           0.040                                         HBS-1                           0.10                                          HBS-3                           4.0 × 10.sup.-3                         Gelatin                         0.80                                          Ninth Layer (high-sensitivity green-sensitive                                 emulsion layer)                                                               Silver iodobromide Emulsion I                                                                         as silver                                                                             1.25                                          ExS-4                           3.7 × 10.sup.-5                         ExS-5                           8.1 × 10.sup.-5                         ExS-6                           3.2 × 10.sup.-4                         ExC-1                           0.010                                         ExM-1                           0.020                                         ExM-4                           0.025                                         ExM-5                           0.040                                         Cpd-3                           0.040                                         HBS-1                           0.25                                          Polyethylacrylate latex         0.15                                          Gelatin                         1.33                                          Tenth Layer (yellow filter layer)                                             Yellow colloidal silver as silver                                                                             0.015                                         Cpd-1                           0.16                                          Solid Disperse Dye ExF-5        0.060                                         Solid Disperse Dye ExF-6        0.060                                         Oil-Soluble Dye ExF-7           0.010                                         HBS-1                           0.60                                          Gelatin                         0.60                                          Eleventh Layer (low-sensitivity blue-sensitive                                emulsion layer)                                                               Silver Iodobromide Emulsion J                                                                         as silver                                                                             0.09                                          Silver Iodobromide Emulsion K                                                                         as silver                                                                             0.09                                          ExS-7                           8.6 × 10.sup.-4                         ExC-8                           7.0 × 10.sup.-3                         ExY-1                           0.050                                         ExY-2                           0.12                                          ExY-3                           0.60                                          ExY-4                           0.020                                         Cpd-2                           0.10                                          Cpd-3                           4.0 × 10.sup.-3                         HBS-1                           0.20                                          Gelatin                         1.20                                          Twelfth Layer (high-sensitivity blue-sensitive                                emulsion layer)                                                               Silver Iodobromide Emulsion L                                                                         as silver                                                                             1.00                                          ExS-7                           4.0 × 10.sup.-4                         ExY-2                           0.08                                          ExY-3                           0.12                                          ExY-4                           0.010                                         Cpd-2                           0.10                                          Cpd-3                           1.0 × 10.sup.-3                         HBS-1                           0.070                                         Gelatin                         0.70                                          Thirteenth Layer (first protective layer)                                     UV-1                            0.19                                          UV-2                            0.075                                         UV-3                            0.065                                         HBS-1                           5.0 × 10.sup.-2                         HBS-4                           5.0 × 10.sup.-2                         Gelatin                         1.8                                           Fourteenth Layer (second protective layer)                                    Silver Iodobromide Emulsion M                                                                         as silver                                                                             0.10                                          H-1                             0.40                                          B'-1 (diameter: 1.7 μm)      5.0 × 10.sup.-2                         B'-2 (diameter: 1.7 μm)      0.15                                          B'-3                            0.05                                          S-1                             0.20                                          Gelatin                         0.70                                          ______________________________________                                    

Further, in order to provide good preservability, processability,pressure durability, antimold/bactericidal property, antistatic propertyand coatability, W-1, W-2, W-3, B'-4, B'-5, B'-6, F-1, F-2, F-3, F-4,F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17,iron salt, lead salt, gold salt, platinum salt, palladium salt, iridiumsalt or rhodium salt was appropriately added to each layer.

Emulsions A to M used in Sample 1001 were the same as Emulsions A to Mused in Sample 401 of Example 4.

Preparation of Dispersion Product of Organic Solid Disperse Dye:

Solid Disperse Dye ExF-2 was dispersed in the same manner as in Example4.

Solid dispersion products of ExF-3, ExF-4 and ExF-6 each was obtained inthe same manner. The average particle size of dye fine particles was0.24, 0.45 or 0.52 μm, respectively. ExF-5 was dispersed by themicroprecipitation dispersion method described in Example 1 ofEP-A-549489. The average particle size was 0.06 μm.

The chemical formulae of additives used in Sample 1001 were the same asthe chemical formulae of additives used in Sample 401 of Example 4.

Each of the thus-prepared photographic material was cut into a size of24 mm (width)×160 cm. At the portion 0.7 mm distant from one side widthdirection in the length direction of the photographic material, twoperforations of 2 mm square were provided at a distance of 5.8 mm. Apair of two perforations was provided at a distance of 32 mm. Then, eachfilm was housed in a plastic-made film cartridge described in FIGS. 1 to7 of U.S. Pat. No. 5,296,887.

On each of these samples, FM signals were recorded from the magneticrecording layer-coated surface side between perforations at a feedingrate of 1,000/s using a head having a head gap of 5 μm and a turn numberof 2,000 and capable of inputting/outputting.

After recording of FM signals, each sample was exposed to light of 1,000cms uniformly throughout the emulsion surface and then processed by thefollowing method. Thereafter, each sample was again housed in the filmcartridge where it had been housed.

Sample 1001 was cut into a width of 35 mm, used for photographing by acamera and processed in the following manner at a processing rate of 1m² /day over 15 days (running processing).

Each processing was conducted as follows using an automatic developingmachine FP-360B manufactured by Fuji Photo Film Co., Ltd. The machinewas modified so that the overflow solution of the bleaching bath did notflow into the post-bath but all was discharged to the waste water tank.On this FP-360B, an evaporation correcting means described in JIIIJournal of Technical Disclosure, No. 94-4992 was mounted.

The processing steps and the composition of each processing solution aredescribed below.

    ______________________________________                                        (Processing Step)                                                                                  Processing                                                                              Replenish-                                                                            Tank                                              Process-  Temperature                                                                             ing Amount*                                                                           Volume                                 Step       ing Time  (°C.)                                                                            (ml)    (l)                                    ______________________________________                                        Color development                                                                        3 min 5 sec                                                                             38.0      20      17                                     Bleaching  50 sec    38.0      5       5                                      Fixing (1) 50 sec    38.0      --      5                                      Fixing (2) 50 sec    38.0      8       5                                      Water washing                                                                            30 sec    38.0      17      3.5                                    Stabilization (1)                                                                        20 sec    38.0      --      3                                      Stabilization (2)                                                                        20 sec    38.0      15      3                                      Drying     1 min 30 sec                                                                            60                                                       ______________________________________                                         *Replenishing amount was per 1.1 m of the 35 mmwidth photographic materia     (corresponding to 1 roll of 24 Ex.).                                     

The stabilizing solution was in a countercurrent system of from (2) to(1) and the overflow solution of washing water was all introduced intothe fixing (2). The fixing solution was also flown from (2) to (1)connected by countercurrent piping. The carried-over amounts ofdeveloper into the bleaching step, of bleaching solution into the fixingstep, of fixing solution into the water washing step were 2.5 ml, 2.0 mland 2.0 ml, respectively, per 1.1 m of the 35 mm-width photographicmaterial. The cross-over time was 6 seconds in each interval and thistime is included in the processing time of the previous step.

The open area of the above-described processing machine was 100 cm² forthe color developer, 120 cm² for the bleaching solution and about 100cm² for other processing solutions.

The composition of each processing solution is shown below.

    ______________________________________                                                            Tank                                                                          Solution                                                                              Replenisher                                                           (g)     (g)                                               ______________________________________                                        (Color Developer)                                                             Diethylenetriaminepentaacetic                                                                     2.0     2.0                                               acid                                                                          1-Hydroxyethylidene-1,1-                                                                          2.0     2.0                                               diphosphonic acid                                                             Sodium sulfite      3.9     5.3                                               Potassium carbonate 37.5    39.0                                              Potassium bromide   1.4     0.4                                               Potassium iodide    1.3 mg  --                                                Disodium N,N-bis(2-sulfonato-                                                                     2.0     2.0                                               ethyl) hydroxylamine                                                          Hydroxylamine sulfate                                                                             2.4     3.3                                               2-Methyl-4- N-ethy1-N-(β-                                                                    4.5     6.4                                               hydroxyethyl) amino!aniline                                                   sulfate                                                                       Water to make       1.0     1.0 l                                             pH (adjusted by potassium                                                                         10.05   10.18                                             hydroxide and sulfuric acid)                                                  (Bleaching Solution)                                                          Ammonium 1,3-diamino-                                                                             118     180                                               propanetetraacetato ferrate                                                   monohydrate                                                                   Ammonium bromide    80      115                                               Ammonium nitrate    14      21                                                Succinic acid       40      60                                                Maleic acid         33      50                                                Water to make       1.0     1.0 l                                             pH (adjusted by aqueous ammonia)                                                                  4.4     4.0                                               (Fixing Solution)                                                             Ammonium methanesulfinate                                                                         10      30                                                Ammonium methanethiosulfonate                                                                     4       12                                                Aqueous solution of ammonium                                                                      280 ml  840 ml                                            thiosulfate (700 g/l)                                                         Imidazole           7       20                                                Ethylenediaminetetraacetic acid                                                                   15      45                                                Water to make       1.0     1.0 l                                             pH (adjusted by aqueous ammonia                                                                   7.4     7.45                                              and acetic acid)                                                              ______________________________________                                    

(Washing Water)

Tap water was passed through a mixed bed column filled with an H-typestrongly acidic cation exchange resin (Amberlite IR-120B, produced byRhom and Haas) and an OH-type strongly basic anion exchange resin(Amberlite IR-400, produced by the same company) to reduce the calciumand magnesium ion concentrations each to 3 mg/l or less and then thereto20 mg/l of sodium isocyanurate dichloride and 150 mg/l of sodium sulfatewere added. The resulting solution had a pH of from 6.5 to 7.5.

    ______________________________________                                        The tank solution and the replenisher were common.                            (Stabilizing Solution)  (unit: g)                                             ______________________________________                                        Sodium p-toluenesulfinate                                                                             0.03                                                  Polyoxyethylene-p-monononylphenyl ether                                                               0.2                                                   (average polymerization degree: 10)                                           Disodium ethylenediaminetetraacetate                                                                  0.05                                                  1,2,4-Triazole          1.3                                                   1,4-Bis(1,2,4-triazol-1-ylmethyl)-                                                                    0.75                                                  piperazine                                                                    1,2-Benzoisothiazolin-3-one                                                                           0.10                                                  Water to make           1.0 l                                                 pH                      8.5                                                   ______________________________________                                    

Evaluation was conducted by adding Compound B-1, B-2, B-3, B-7, B-11,B-16 or B-40 for use in the present invention to the red-sensitivelayer. In samples where the compound for use in the present inventionwas added, the fluctuation in the photographic property was smallbetween the sample processed immediately after exposure and the samplesstored under forcedly deteriorating conditions, as compared with thesample where the compound was not added (Sample 1001).

Further, there was no difference in the change in the photographicproperty of the red-sensitive layer between samples where the compoundfor use in the present invention was added and the sample where thecompound for use in the present invention was not added.

Also, when the compound for use in the present invention was added tothe green-sensitive layer, an excellent effect was provided on theimprovement of storability after exposure.

EXAMPLE 11

Samples were prepared by adding Compound B-4, B-27 or B-28 for use inthe present invention in an amount of 5×10⁻² mol/mol-Ag to the fourth,fifth and sixth layers of Sample 701 in Example 7 of JP-A-6-118533. Eachsample was exposed and then allowed to stand under forcedlydeteriorating conditions of 50° C. and 60% for 7 days. Thereafter, eachsample was subjected to color reversal processing described inJP-A-6-118533 (pages 37 and 38) and evaluated. As a result, thephotographic materials to which the compound for use in the presentinvention was added, exhibited advantageous capability such that theincrease in the sensitivity upon leaving after exposure was small andthe reduction in the maximum color density was small, as compared withthe photographic material to which the compound was not added.

EXAMPLE 12

Preparation of Emulsion A

Emulsion A was prepared in the same manner as in Example 6.

Preparation of Emulsion B

Emulsion B was prepared in the same manner as i n Example 6.

Preparation of Coated Samples

Coated Sample 1201 was prepared in the same manner as Coated Sample 601in Example 6.

To 300 ml of ethyl acetate, 18.9 g of Compound B-4 for use in thepresent invention, 19.0 g of poly-t-butylacrylamido (molecular weight:100,000), 9.5 g of high boiling point organic solvent (Solv-1) and 38.0g of surface active agent (W-1) were added and dissolved under heating.The resulting solution was added to a 10% aqueous gelatin solution andemulsion-dispersed in a house-use mixer for 10 minutes.

The emulsified product obtained was added to the third and fourth layersof Sample 1201 so that the coverage of Compound B-4 for use in thepresent invention could be 0.1 mol/mol-Ag, to thereby prepare Sample1203. Sample 1202 was prepared by removing only Compound B-4 for use inthe present invention from the emulsified product of Sample 1203 andSample 1204 was prepared by using Compound B-27 in place of Compound B-4for use in the present invention in Sample 1203.

These samples were stored under temperature and humidity conditions of30° C. and 65% RH for 14 days after the coating. Each sample was testedaccording to the following method.

(1) Measurement of Sensitivity

Each sample was exposed through an optical wedge for 1/100 second usinga tungsten light source having a color temperature of 2854K of whichcolor temperature was increased through a color temperature variationfilter to 5400K.

Then, each sample was subjected to development, fixing, water washingand drying in an automatic developing machine. The sensitivity of eachsample is shown by a logarithm of the reciprocal of an exposure amountrequired to give an optical density 0.5 higher than the fog.

The development conditions are as follows.

    ______________________________________                                                 Processing Solution                                                                       Temperature                                                                             Time                                           ______________________________________                                        Development                                                                              HPD           26.5° C.                                                                         55 sec.                                    Fixing     Super Fujix DP2                                                                             26.5° C.                                                                         76 sec.                                    Water washing                                                                            Flowing water 20° C.                                                                           95 sec.                                    Drying                   50° C.                                                                           69 sec.                                    ______________________________________                                    

The aging stability of photographic property when the photographicmaterial was allowed to stand after photographing was evaluatedaccording to the following method.

Samples 1201 to 1204 were exposed by the above-described method and thenallowed to stand under conditions of 50° C. and 60% for 7 days. Then,each sample was processed and measured according to the method describedabove. The results are shown in Table 6 as a relative value to that ofthe sample processed immediately after exposure. The nearer to 0 thevalue is, the smaller the change due to aging is.

                  TABLE 6                                                         ______________________________________                                                          Aging Stability                                                               after Photographing                                                                 Change in                                                                              Increase                                     Sample     Compound     Sensitivity                                                                            of Fog                                       ______________________________________                                        1201       --           +0.09    0.05                                         (Comparison)                                                                  1202       --           +0.08    0.06                                         (Comparison)                                                                  1203       B-4          +0.01    0.03                                         (Invention)                                                                   1204        B-27        +0.02    0.02                                         (Invention)                                                                   ______________________________________                                    

It is clearly seen from Table 6 that the photographic materialscontaining the compound for use in the present invention wereoutstandingly improved in the aging stability of the photographicproperty when they were left after photographing.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A silver halide photographic material comprisinga support having thereon at least one light-sensitive silver halideemulsion layer, wherein said silver halide photographic materialcontains a compound represented by formula (IA): ##STR109## whereinR^(1a) represents a hydrogen atom, a substituted or unsubstituted alkylgroup having from 1 to 20 carbon atoms, a substituted or unsubstitutedalkenyl group having from 2 to 20 carbon atoms or a substituted orunsubstituted aryl group having from 6 to 20 carbon atoms;R^(2a)represents an alkenyl group having a total carbon number of 4 or more ora cycloalkenyl group having a total carbon atom number of 6 or more;provided that when R^(2a) is a styryl group, R^(1a) is a substituted orunsubstituted alkyl group having from 1 to 20 carbon atoms, asubstituted or unsubstituted alkenyl group having from 2 to 20 carbonatoms or a substituted or unsubstituted aryl group having from 6 to 20carbon atoms; and when R^(2a) is an alkenyl group having a total carbonnumber of 17 or more, R^(1a) is a hydrogen atom, a substituted orunsubstituted alkyl group having 7 or more carbon atoms, a substitutedor unsubstituted alkenyl group having 7 or more carbon atoms or asubstituted or unsubstituted aryl group having from 6 to 20 carbonatoms.
 2. A silver halide photographic material as claimed in claim 1,wherein the compound represented by formula (IA) has a structurerepresented by formula (IIA) or (IIIA): ##STR110## wherein in formula(IIA), R^(1a) represents a hydrogen atom, a substituted or unsubstitutedalkyl group having from 1 to 20 carbon atoms or a substituted orunsubstituted alkenyl group having from 2 to 20 carbon atoms;Q^(1a)represents an atomic group necessary for forming a cycloalkenyl group bycombining with the carbon atoms at both terminals; R^(3a) and R^(4a),which may be the same or different, each represents an alkyl grouphaving from 1 to 22 carbon atoms, an aryl group having from 6 to 20carbon atoms, an alkenyl group having from 3 to 22 carbon atoms, acarboxyl group, a cyano group, an acyl group having from 2 to 20 carbonatoms, an aminocarbonyl group having from 1 to 37 carbon atoms, analkoxycarbonyl group having from 2 to 20 carbon atoms, anaryloxycarbonyl group having from 7 to 20 carbon atoms or a heterocyclicgroup having from 3 to 20 carbon atoms; R^(a) represents an alkyl group,an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, acarboxyl group, a cyano group, a sulfamoyl group, an acyl group, acarbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, anacylamino group, an alkoxycarbonylamino group, an aryloxycarbonylaminogroup, an alkylsulfonylamino group, an arylsulfonylamino group, anaminocarbonylamino group, a sulfamoylamino group, an amino group, aheterocyclic oxy group, an alkylthio group, an arylthio group, aheterocyclic thio group, a heterocyclic group, an alkylsulfonyl group oran arylsulfonyl group; and na represents 0 or a positive integer, andwhen na is 0, R^(a) is a hydrogen atom and when na is 2 or greater, theR^(a) groups in plurality may be the same or different; and in formula(IIIA), R^(1a) represents a hydrogen atom, a substituted orunsubstituted alkyl group having from 1 to 20 carbon atoms or asubstituted or unsubstituted alkenyl group having from 2 to 20 carbonatoms, R^(3a), R^(4a) and R^(5a), which may be the same or different,each has the same meaning as R^(3a) or R^(4a) of formula (IIA); whenR^(4a) is a phenyl group, R^(1a) is a substituted or unsubstituted alkylgroup having from 1 to 22 carbon atoms, a substituted or unsubstitutedalkenyl group having from 2 to 22 carbon atoms or a substituted orunsubstituted aryl group having from 6 to 20 carbon atoms; and R^(3a)and R^(4a) and/or R^(4a) and R^(5a) and/or R^(5a) and R^(1a) may becombined with each other to form a 5- or 6-membered ring structure.
 3. Asilver halide photographic material as claimed in claim 1, wherein thecompound represented by formula (IA) has a structure represented byformula (IVA) or (VA): ##STR111## wherein in formula (IVA), R^(1a),R^(3a) and R^(4a) have the same meaning as R^(1a), R^(3a) and R^(4a) offormula (IIA) in claim 2, respectively;R^(6a), R^(7a), R^(8a), R^(9a),R^(10a), R^(11a), and R^(12a), which may be the same or different, eachrepresents a hydrogen atom, an alkyl group having from 1 to 20 carbonatoms, an alkoxycarbonyl group having from 2 to 30 carbon atoms, anaminocarbonyl group having from 1 to 30 carbon atoms or anaryloxycarbonyl group having from 7 to 30 carbon atoms; and in formula(VA), R^(1a) has the same meaning as R^(1a) of formula (IIIA) in claim2; R^(3a), R^(4a) and R^(5a), which may be the same or different, eachrepresents a hydrogen atom, an alkyl group having from 1 to 20 carbonatoms, an aryl group having from 6 to 22 carbon atoms, an alkoxycarbonylgroup having from 2 to 30 carbon atoms, an aryloxycarbonyl group havingfrom 7 to 30 carbon atoms or an aminocarbonyl group having from 1 to 30carbon atoms; and when R^(4a) is a phenyl group, R^(1a) is a substitutedor unsubstituted alkyl group having from 1 to 20 carbon atoms or asubstituted or unsubstituted alkenyl group having from 2 to 20 carbonatoms.
 4. A silver halide photographic material as claimed in claim 3,wherein the compound represented by formula (IA) has a structurerepresented by formula (IVA).
 5. A silver halide photographic materialas claimed in claim 3, wherein the compound represented by formula (IA)has a structure represented by formula (VA).
 6. A silver halidephotographic material comprising a support having thereon at least onesilver halide emulsion layer, which contains at least one hydroxamicacid compound having a bicyclo ring as a partial structure, wherein saidhydroxamic acid compound is represented by the following formula (IB):##STR112## wherein R^(1b) represents a hydrogen atom, a substituted orunsubstituted alkyl group having from 1 to 30 carbon atoms, asubstituted or unsubstituted cycloalkyl group having from 5 to 30 carbonatoms, a substituted or unsubstituted alkenyl group having from 3 to 30carbon atoms or a substituted or unsubstituted cycloalkenyl group havingfrom 5 to 30 carbon atoms, and R^(2b) represents a substituted orunsubstituted bicycloalkyl group having from 5 to 40 carbon atoms or asubstituted or unsubstituted bicycloalkenyl group having from 5 to 40carbon atoms.
 7. A silver halide photographic material as claim in claim6, wherein the compound represented by formula (IB) has a structurerepresented by formula (IIB) or (IIIB): ##STR113## wherein R^(1b)represents a hydrogen atom, a substituted or unsubstituted alkyl grouphaving from 1 to 30 carbon atoms, a substituted or unsubstitutedcycloalkyl group having from 5 to 30 carbon atoms, a substituted orunsubstituted alkenyl group having from 3 to 30 carbon atoms or asubstituted or unsubstituted cycloalkenyl group having from 5 to 30carbon atoms;R^(3b) and R^(4b), which may be the same or different, eachrepresents a hydrogen atom or a substituted or unsubstituted alkyl grouphaving from 1 to 30 carbon atoms; and Q^(1b), Q^(2b) and Q^(3b) eachindependently represents an atomic group necessary for forming a bicycloring by combining with the carbon atoms at both terminals.
 8. A silverhalide photographic material as claimed in claim 6, wherein the compoundrepresented by formula (IB) has a structure represented by formula (IVB)or (VB): ##STR114## wherein X^(b) represents --OR^(5b) or --N(R^(5b))(R^(6b)) (wherein R^(5b) and R^(6b), which may be the same or different,each represents a hydrogen atom, a substituted or unsubstituted alkylgroup having from 1 to 30 carbon atoms, a substituted or unsubstitutedcycloalkyl group having from 5 to 30 carbon atoms or a substituted orunsubstituted aryl group having from 6 to 30 carbon atoms, and R^(5b)and R^(6b) are combined with each other to form a ring structure);andR^(1b) represents a hydrogen atom or an alkyl group having from 1 to6 carbon atoms.
 9. A silver halide photographic material as claimed inclaim 8, wherein the compound represented by formula (IB) has astructure represented by formula (IVB).
 10. A silver halide photographicmaterial as claimed in claim 8, wherein the compound represented byformula (IB) has a structure represented by formula (VB).